self cooling container and a cooling device

ABSTRACT

The present invention relates to a container for storing a beverage, the container having a container body and a closure and defining an inner chamber, the inner chamber defining an inner volume and including a specific volume of the beverage. The container further includes a cooling device having a housing defining a housing volume. The cooling device includes at least two separate, substantially non-toxic reactants causing an entropy-increasing reaction producing substantially non-toxic products in a stoichiometric number. The at least two separate substantially non-toxic reactants initially being included in the cooling device are separated from one another and causing an entropy-increasing reaction and a heat reduction of the beverage of at least 50 Joules/ml beverage. The cooling device further includes an actuator for initiating the reaction between the at least two separate, substantially non-toxic reactants.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a national phase filing, under 35 U.S.C. §371(c), ofInternational Application No. PCT/EP2009/066703, filed Dec. 9, 2009, thedisclosure of which is incorporated herein by reference in its entirety.This application is also related to commonly assigned U.S. ApplicationSerial No. 13/133,621, filed Jun. 8, 2011, entitled “A SYSTEM AND METHODFOR PROVIDING A SELF COOLING CONTAINER.”

FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not Applicable

BACKGROUND

Beverage cans and beverage bottles have been used for decades forstoring beverages, such as carbonated beverages, including beer, cider,sparkling wine, carbonated mineral water or various soft drinks, oralternatively non-carbonated beverages, such as non-carbonated water,milk products such as milk and yoghurt, wine or various fruit juices.The beverage containers, such as bottles and in particular cans, aretypically designed for accommodating a maximum amount of beverage, whileminimising the amount of material used, while still ensuring themechanical stability of the beverage container.

Most beverages have an optimal serving temperature significantly belowthe typical storage temperature. Beverage containers are typicallystored at room temperatures in supermarkets, restaurants, private homesand storage facilities. The optimal consumption temperature for mostbeverages is around 5° C. and therefore, cooling is needed beforeserving the beverage. Typically, the beverage container is positioned ina refrigerator or a cold storage room or the like well in advance ofserving the beverage so that the beverage may assume a temperature ofabout 5° C. before serving. Persons wishing to have a beverage readilyavailable for consumption must therefore keep their beverage stored at alow temperature permanently. Many commercial establishments such asbars, restaurants, supermarkets and petrol stations require constantlyrunning refrigerators for being able to satisfy the customers' need ofcool beverage. This may be regarded a waste of energy since the beveragecan may have to be stored for a long time before being consumed. In thepresent context, it should be mentioned that the applicant company aloneinstalls approximately 17000 refrigerators a year for providing coolbeverages, and each refrigerator typically has a wattage of about 200 W.

As discussed above, the cooling of beverage containers by means ofrefrigeration is very slow and constitutes a waste of energy. Somepersons may decrease the time needed for cooling by storing the beveragecontainer for a short period of time inside a freezer or similar storagefacility having a temperature well below the freezing point. This,however, constitutes a safety risk because if the beverage container isnot removed from the freezer well before it freezes, it may cause arupture in the beverage can due to the expanding beverage.Alternatively, a bucket of ice and water may be used for a moreefficient cooling of beverage since the thermal conductivity of water issignificantly above the thermal conductivity of air.

It would be advantageous if the beverage container itself contains acooling element, which may be activated shortly before consuming thebeverage for cooling the beverage to a suitable low temperature. Withinthe beverage field of packaging, a particular technique relating tocooling of beverage cans and self-cooling beverage cans have beendescribed in among others U.S. Pat. No. 4,403,567, U.S. Pat. No.7,117,684, EP0498428, U.S. Pat. No. 2,882,691, GB2384846, WO2008000271,GB2261501, U.S. Pat. No. 4,209,413, U.S. Pat. No. 4,273,667, U.S. Pat.No. 4,303,121, U.S. Pat. No. 4,470,917, U.S. Pat. No. 4,689,164,US20080178865, JP2003207243, JP2000265165, U.S. Pat. No. 3,309,890,WO8502009, U.S. Pat. No. 3,229,478, U.S. Pat. No. 4,599,872, U.S. Pat.No. 4,669,273, WO2000077463, EP87859 (fam U.S. Pat. No. 4,470,917), U.S.Pat. No. 4,277,357, DE3024856, U.S. Pat. No. 5,261,241 (fam EP0498428),GB1596076, U.S. Pat. No. 6,558,434, WO02085748, U.S. Pat. No. 4,993,239,U.S. Pat. No. 4,759,191, U.S. Pat. No. 4,752,310, WO0110738, EP1746365,U.S. Pat. No. 7,117,684, EP0498428, U.S. Pat. No. 4,784,678, US2746265,US1897723, US2882691, GB2384846, U.S. Pat. No. 4,802,343, U.S. Pat. No.4,993,237, WO2008000271, GB2261501, US20080178865, JP2003207243, U.S.Pat. No. 3,309,890, U.S. Pat. No. 3,229,478, WO2000077463, WO02085748.

The above-mentioned documents describe technologies for generatingcooling via a chemical reaction, alternatively via vaporisation. Forusing such technologies as described above, an instant cooling can beprovided to a beverage and the need of pre-cooling and consumption ofelectrical energy is avoided. Among the above technologies, the coolingdevice is large in comparison with the beverage container. In otherwords, a large beverage container has to be provided for accommodating asmall amount of beverage resulting in a waste of material and volume.Consequently, there is a need for cooling devices generating morecooling and/or occupying less space within the beverage container.

SUMMARY

An object of the present invention is to provide a cooling device whichmay be used inside a beverage container for reducing the temperature ofa beverage from about 22° C. to about 5° C., thereby eliminating or atleast substantially reducing the need of electrical powered externalcooling.

A further advantage according to the present invention is that thebeverage container and the cooling device may be stored for an extendedtime such as weeks, months or years until shortly before the beverage isabout to be consumed at which time the cooling device is activated andthe beverage is cooled to a suitable consumption temperature. It istherefore a further object of the present invention to provideactivators for activating the cooling device shortly before the beverageis about to be consumed.

The above objects together with numerous other objects which will beevident from the below detailed description of preferred embodiments ofthe cooling device according to the present invention and are accordingto a first aspect of the present invention obtained by a container forstoring a beverage, the container having a container body and a closureand defining an inner chamber, the inner chamber defining an innervolume and including a specific volume of the beverage,

-   -   the container further including a cooling device having a        housing defining a housing volume not exceeding approximately        33% of the specific volume of the beverage and further not        exceeding approximately 25% of the inner volume,    -   the cooling device including at least two separate,        substantially non-toxic reactants causing when reacting with one        another a non-reversible, entropy-increasing reaction producing        substantially non-toxic products in a stoichiometric number at        least a factor 3, preferably at least a factor 4, more        preferably at least a factor 5 larger than the stoichiometric        number of the reactants,    -   the at least two separate substantially non-toxic reactants        initially being included in the cooling device separated from        one another and causing, when reacting with one another in the        non-reversible, entropy-increasing reaction, a heat reduction of        the beverage of at least 50 Joules/ml beverage, preferably at        least 70 Joules/ml beverage, such as 70-85 Joules/ml beverage,        preferably approximately 80-85 Joules/ml, within a period of        time of no more than 5 min. preferably no more than 3 min., more        preferably no more than 2 min., and    -   the cooling device further including an actuator for initiating        the reaction between the at least two separate, substantially        non-toxic reactants.

The container is typically a small container intended for one servinghaving a volume of about 20 to 75 centilitres of beverage. In somecases, however, it may be decided to use a cooling device with a largercontainer, such as a large bottle or vessel, which may accommodate onelitre of beverage or a keg, which may accommodate five litres or more ofbeverage. In such cases, a cooling device is intended to give thebeverage an instant cooling to suitable consumption temperature for thefirst serving of beverage, where after the beverage may be kept in arefrigerator for subsequent servings. The container is preferably madeof aluminium, which is simple to manufacture, i.e. by stamping, andwhich may be recycled in an environmentally friendly way by melting ofthe container. Alternatively, collapsible or non-collapsible containersmay be manufactured in polymeric materials such as PET plastics. Yetalternatively, the container may be a conventional glass bottle.

The cooling device is preferably fixated to the beverage container, suchas fixated to the bottom of the container or the lid of the container.The cooling device should have a housing for separating the beverage andthe reactant. The cooling device should not require a too large portionof the inner volume of the beverage container, since a too large coolingdevice will result in a smaller amount of beverage being accommodated inthe beverage container. This would require either larger beveragecontainers or alternatively more beverage containers being produced foraccommodating the same amount of beverage, both options beingecologically and economically undesired due to more raw material beingused for manufacturing containers and more storage and transportationvolume. It has been contemplated that a cooling device housing volume ofabout 33% of the beverage volume and 25% of the total inner volume ofthe beverage container would be still acceptable trade off betweencooling efficiency and accommodated beverage volume. A too small coolingdevice would not be able to cool the beverage to sufficiently lowtemperatures.

The two reactants used in the cooling device should be held separatelybefore activation of the cooling device and when the cooling device isactivated, the two reactants are caused to react with one another. Thereactants may be held separately by for instance being accommodated intwo separated chambers or alternatively, one or both of the reactantsmay be provided with a coating preventing any reaction to start untilactivation. The two reactants should be substantially non-toxic, whichwill be understood to mean non-fatal if accidentally consumed in therelevant amounts used in the cooling device. It is further contemplatedthat there may be more than two reactants, such as three or morereactants. The reaction should be an entropy increasing reaction, i.e.the number of reaction products should be larger than the number ofreactants. In the present context it has surprisingly been found outthat an entropy increasing reaction producing products of astoichiometric number of at least three, preferably four or more,preferably five larger than the stoichiometric number of the reactantswill produce a more efficient cooling than a smaller stoichiometricnumber. The stoichiometric number is the relationship between the numberof products divided with the number of reactants. The reaction should benon-reversible, i.e. understood to mean it should not withoutsignificant difficulties be possible to reverse the reaction, whichwould cause a possible reheating of the beverage. The temperature of thebeverage should be reduced by at least 15° C. or preferably 20° C.,which for a water-based beverage corresponds to a heat reduction of thebeverage of about 50 to 85 joules per liter of beverage. Any smallertemperature or heat reduction would not yield a sufficient cooling tothe beverage, and the beverage would be still unsuitably warm when thechemical reaction has ended and the beverage is about to be consumed.Preferably, the chemical reaction produces a heat reduction of 120-240J/ml of reactants, or most preferably 240-330 J/ml of reactants. Suchcooling efficiency is approximately the cooling efficiency achieved bymelting of ice into water. The chemical reaction should preferably be asquick as possible, however still allowing some time for the thermalenergy transport for avoiding ice formation near the cooling device. Ithas been contemplated that preferably the heat or temperature reductionis accomplished within no more than five minutes or preferably no morethan two minutes. These are time periods which are acceptable beforebeverage consumption. In the present context it may be noted thatcarbonated beverages typically allow a lower temperature of the coolingdevice compared to non-carbonated beverages since the formation of CO₂bubbles rising in the beverage will increase the amount of turbulence inthe beverage and therefore cause the temperature to equalize fasterwithin the beverage.

Further, the term non-reversible should be considered to be synonymouswith the word irreversible. The term non-reversible reaction should beunderstood to mean a reaction in which the reaction products and thereactants do not form a chemical equilibrium which is reversible bysimply changing the proportions of the reactants and/or the reactionproducts and/or the external conditions such as pressure, temperatureetc. Examples of non-reversible reactions include reactions in which thereaction products constitute a complex, a precipitation or a gas.Chemical reactions, such as reactions involving dissolving of a salt ina liquid such as water and disassociation of the salt into ions, whichform an equilibrium, will come to a natural stop when the forwardreaction and the backward reaction proceed at equal rate. E.g. in mostsolutions or mixtures the reaction is limited by the solubility of thereactants. A non-reversible reaction as defined above will continueuntil all of the reactants have reacted.

German published patent application DE 21 50 305 A1 describes a methodfor cooling beverage bottles or cans. A cooling cartridge including asoluble salt is included in the bottle or can. By dissolving the salt ina specific volume of water a cooling effect is obtained by utilizing thenegative solution enthalpy. However, by using the negative solutionenthalpy as proposed, the lowest temperature achieved was about 12° C.,assuming an initial temperature of 21° C. None of the examples ofembodiments achieves the sought temperature of about 5° C. Bycalculating the heat reduction in the beverage (Q=c*m*ΔT), the exampleembodiments achieve heat reductions of only about 15-38 J/ml ofbeverage. All of the examples of embodiments also require reactantshaving a total volume exceeding 33% of the beverage volume. Further, allof the reactions proposed in the above-mentioned document are consideredas reversible, since the reactions may be reversed by simply removingthe water from the solution. By removing the water, the dissolved saltions will recombine and form the original reactants.

The German utility model DE 299 11 156 U1 discloses a beverage canhaving an external cooling element. The cooling element may be activatedby applying pressure to mix two chemicals located therein. The documentonly describes a single chemical reaction including dissolving anddisassociation of potassium chloride, saltpeter and salmiac salt inwater which is stated to reach a temperature of 0° C. or even −16° C. ofthe cooling element, although the description is silent about thestarting temperature of the cooling element. The description is alsosilent about the dimensions used for the cooling element and whichvolumes of beverage and reactants are used.

Many non-reversible entropy increasing reactions are known as such. Oneexample is found on the below internet URL:http://web.archive.org/web/20071129232734/http://chemed.chem.purdue.edu/demo/demosheets/5.1.html.The above reference suggests the below reaction:

-   -   Ba(OH)₂.8H₂O(s)+2NH₄SCN(s)→Ba(SCN)₂+2NH₃(g)+10H₂O(l)

The above reference suggests that the reaction above is endothermal andentropy increasing and generates a temperature below the freezingtemperature of water. However, there is no indication that the abovereaction may be used in connection with the cooling of beverage, nor isany information about the amounts of reactants required available, northe use of an actuator to initiate the reaction.

Different from most solution reactions, it should be noted that theabove reaction may be initiated without the addition of any liquidwater. Some other non-reversible entropy increasing reactions requireonly a single drop of water to initiate.

The use of ammonia is in the present context not preferred, sinceammonia may be considered toxic, and will, in case it escapes into thebeverage, yield a very unpleasant taste to the beverage. Preferably, allreactants as well as reaction products should in addition to beingnon-toxic have a neutral taste in case of accidental release into thebeverage.

An actuator is used for activating the chemical reaction between thereactants. A reactant may include a pressure transmitter fortransmitting a pressure increase, or alternatively a pressure drop, fromwithin the beverage container to the cooling device for initiating thereaction. The pressure drop is typically achieved when the beveragecontainer is open, thus the cooling device may be arranged to activatewhen the beverage container is being opened, alternatively, a mechanicalactuator may be used to initiate the chemical reaction. The mechanicalactuator may constitute a string or a rod or communicate with theoutside of the beverage container for activating the chemical reaction.Alternatively, the mechanical actuator may be mounted in connection withthe container closure so that when the container is opened, a chemicalreaction is activated. The activation may be performed by bringing thetwo reactants in contact with each other, i.e. by providing thereactants in different chambers provided by a breakable, dissolvable orrupturable membrane, which is caused to break, dissolve or rupture bythe actuator. The membrane may for instance be caused to rupture by theuse of a piercing element. The reaction products should, as well as thereactants be substantially non-toxic.

One kind of activator is disclosed in the previously mentioned DE 21 50305 A1, which uses a spike to penetrate a membrane separating the twochemicals. US 2008/0016882 shows further examples of activators havingthe two chemicals separated by a peelable membrane or a small conduit.

The volume of the products should not substantially exceed the volume ofthe reactants, since otherwise, the cooling device may be caused toexplode during the chemical reaction. A safety margin of 3 to 5%, oralternatively a venting aperture, may be provided. A volume reductionshould be avoided as well. The reactants are preferably provided asgranulates, since granulates may be easily handled and mixed. Thegranulates may be provided with a coating for preventing reaction. Thecoating may be dissolved during activation by for instance a liquidentering the reaction chamber and dissolving the coating. The liquid maybe referred to as an activator and may constitute e.g. water, propyleneglycol or an alcohol. It is further contemplated that a reactioncontrolling agent, such as a selective adsorption controlling agent or aretardation temperature setting agent may be used for reducing thereaction speed, alternatively, a catalyst may be used for increasing thereaction speed. It is further contemplated that a container may compriseguiding elements for guiding the flow of beverage towards the coolingdevice for increasing the cooling efficiency. The present cooling devicemay also be used in a so-called party keg, which is a beverage keghaving internal pressurization and dispensing capabilities. In this way,the comparatively large party kegs must not be pre-cooled before beingused. The cooling device may alternatively be provided as a widget whichis freely movable within the container. This may be suitable for glassbottles where it may be difficult to provide a fixated cooling device.

According to a further embodiment of the first aspect of the presentinvention, the two separate reactants comprise one or more salthydrates. Salt hydrates are known for producing an entropy increasingreaction by releasing water molecules. In the present context, aproof-of-concept has been made by performing a laboratory experiment. Inthe above-mentioned laboratory experiment, a dramatic energy change hasbeen established by causing two salts, each having a large number ofcrystal water molecules added to the structure, to react and liberatethe crystal water as free water. In the present laboratory experiment,the following chemical reaction has been tried out: Na₂SO₄, 10H₂O+CaCl₂,6H₂O→2NaCl+CaSO₄, 2H₂O+14H₂O. The left side of the reaction schemeincludes a total of two molecules, whereas the right side of thereaction schemes includes twenty molecules. Therefore, the entropyelement—TΔS becomes fairly large, as ΔS is congruent to k×In20/2.

The above chemical reaction produces a simple salt in an aqueoussolution of gypsum. It is therefore evident that all constituents inthis reaction are non-toxic and non-polluting. In the presentexperiment, 64 grams of Na₂SO₄ and 34 grams of CaCl₂, the reaction hasproduced a temperature reduction of 20° C., which has been maintainedstable for more than two hours. A prototype beer can has beenmanufactured having a total volume of 450 ml including 330 ml of beerand a bottle of 100 ml including the two reactants. After the opening ofthe can, the reactants were allowed to react resulting in a dramaticcooling of the beer inside the beverage can.

According to the present invention, a cooling device is provided basedon a chemical reaction between two or more reactants. The chemicalreaction is a spontaneous non-reversible endothermic reaction driven byan increase in the overall entropy. The reaction absorbs heat from thesurroundings resulting in an increase in thermodynamic potential of thesystem. ΔH is the change in enthalpy and has a positive sign forendothermic reactions. The spontaneity of a chemical reaction can beascertained from the change in Gibbs free energy ΔG.

At constant temperature ΔG=ΔH−T*ΔS. A negative ΔG for a reactionindicates that the reaction is spontaneous. In order to fulfill therequirements of a spontaneous endothermic reaction the overall increasein entropy ΔS for the reaction has to overcome the increase in enthalpyΔH.

According to a further embodiment of the first aspect of the presentinvention at least two separate, substantially non-toxic reactantscomprise a first reactant, a second reactant and a third reactant, thesecond and third reactants being present as separate granulates and thefirst reactant being applied as a coating covering the granulates of thesecond and third reactants. By coating the second and the thirdreactants by the first reactant it can be ensured that the threereactants are held separated although the three reactants are mixed,since the second and the third reactants are prevented from reacting bythe first reactant. In this way accidental activation of the chemicalreaction may be avoided, e.g. by shock or in case a small amount ofwater enters the reaction chamber, the reaction will not be initiatedsince the coating will protect the second and third reactants. It ispreferred to use the first reactant as the coating, since a non-reactingcoating would constitute a waste of volume and thereby necessitate alarger cooling device.

According to a further embodiment of the first aspect of the presentinvention the second and third reactants generate a first non-reversibleentropy increasing reaction producing an intermediate reaction product,and the third reactant reacting with the intermediate reaction productgenerating a second non-reversible entropy increasing reaction. In casethe intermediate reaction products are toxic or otherwise unpleasant,such as bad smelling, the negative effect of the intermediate productsmay be avoided by allowing them to react with the third reactant andcreate an end product which is safe and which does not have any of thedrawbacks of the intermediate reaction products.

According to a further embodiment of the first aspect of the presentinvention the intermediate product is a gas and the secondnon-reversible entropy increasing reaction generates a complex or aprecipitate. For instance, the intermediate product may be a toxic orsmelly gas, which may be unsuitable for use in the present context. Thegas may then be pacified by reacting with the third reactant to form acomplex or a precipitate which is safe.

According to a further embodiment of the first aspect of the presentinvention the first reactant is dissolvable by water or an organicsolvent preferably a liquid such as water, the first, second and thirdreactants being prevented from reacting through the coating. Uponinitiation, a sufficient amount of water to at least partially dissolvethe coating is introduced into the cooling device, thereby allowing allthree reactants to dissolve and react with each other.

According to a further embodiment of the first aspect of the presentinvention the cooling device is accommodated within the container. Toensure that a high percentage of the cooling energy is used for coolingthe beverage and not lost to the surroundings, the cooling device may belocated within the container, preferably in direct contact with thebeverage and more preferably completely surrounded by beverage.

Reactants

The cooling device according to the present invention includes at leasttwo separate, substantially non-toxic reactants causing with one anothera non-reversible entropy increasing reaction producing substantiallynon-toxic products in a stoichiometric number at least a factor 3,preferably a factor 4, more preferably a factor 5 larger than thestoichiometric number of the reactants.

The reactants are preferably solids but solid-liquid, liquid-liquid andsolid-solid-liquid reactants are contemplated also to be relevant in thepresent context i.e. in the context of implementing a cooling device foruse in a beverage container. Solid reactants may be present as powder,granules, shavings, etc.

The reactants and products are substantially non-toxic.

In the context of the present invention non-toxic is not to beinterpreted literally but should be interpreted as applicable to anyreactant or product which is not fatal when ingested in the amounts andforms used according to the present invention. Suitable reactants formproducts which are a) easily soluble in the deliberated crystal water orb) insoluble in the deliberated crystal water. A list of easily solublevs less soluble salt products is given below:

Easily soluble Less soluble NaCl BaSO₄ KCl BaCO₃ NH₄Cl Bi(OH)₃ NH₄BrCaCO₃ NH₄C₂H₃O₂ Ca₃(PO₄)₂ NH₄NO₃ CaSO₄•2H₂0 (NH₄)₂SO₄ CoCO₃ NH₄HSO₄Co(OH)₂ CaCl₂ CuBr CrCl₂ Cu(OH)₂ CuBr₂ Fe(OH)₂ LiBr•2H₂O Fe(OH)₃LiCl•H₂O FePO₄•2H₂O NH₂OH Fe₃(PO₄)₂ KBr Li₂CO₃ KCO₃•1½H₂O MgCO₃ KOH•2H₂OMnCO₃ KNO₃ Mn(OH)₂ KH₂PO₃ Ni(OH)₂ KHSO₄ SrCO₃ NaBr₂ 2H₂O SrSO₄ NaClO₃Sn(OH)₂ NaOH•H₂O ZnCO₃ NaNO₃ Zn(OH)₂ NaSCN SnSO₄ TiCl₃ TiCl₄ ZnBr₂•2H₂OZnCl₂ NH₄SCN

Further suitable reactants are the following:

NaAl(SO₄)_(2.) 12H₂0 NH₄Al(SO₄)_(2.) 12H₂0 LiOH H₂0 Na₂SiO₃

Na₂SiO₃.xH₂0, x=5-9Na₂O.xSiO₂, x=3-5

Na₄SiO₄ Na₆Si₂O₇ Li₂SiO₃ Li₄SiO₄

Additional reactants and sets of reactants are listed in the below Table1 and Table 2.

The salt product is preferably an easily soluble salt although lesssoluble products are preferable for salt products which are toxic torender them substantially non-toxic.

The volumetric change during the non-reversible entropy-increasingreaction is no more than ±5%, preferably no more than ±4%, furtherpreferably no more than ±3%, or alternatively the cooling device beingvented to the atmosphere for allowing any excess gas produced in thenon-reversible entropy-increasing reaction to be vented to theatmosphere.

Suitable solid reactants according to the present invention are salthydrates and acid hydrates. The salt hydrates according to the inventionare organic salt hydrates or inorganic salt hydrates, preferablyinorganic salt hydrates. Some of the below salts are contemplated to bepresent only in trace amounts for controlling selective adsorption.Suitable organic salt hydrates may include Magnesium picrate octahydrateMg(C₆H₂(NO₂)₃O)₂.8H₂O, Strontium picrate hexahydrateSr(C₆H₂(NO₂)₃O)₂.6H₂O, Sodium potassium tartrate tetrahydrateKNaC₄H₄O₆.4H₂O, Sodium succinate hexahydrate Na₂(CH₂)₂(COO)₂.6H₂O,Copper acetate monohydrate Cu(CH₃COO)₂.H₂O etc. Suitable inorganic salthydrates according to the invention are salt hydrates of alkali metals,such as lithium, sodium and potassium, and salt hydrates of alkalineearth metals, such as beryllium, calcium, strontium and barium, and salthydrates of transition metals, such as chromium, manganese, iron,cobalt, nickel, copper, and zinc, and aluminium salt hydrates andlanthanum salt hydrates. Suitable alkali metal salt hydrates are forexample LiNO₃.3H₂O, Na₂SO₄.10H₂O (Glauber's salt), Na₂SO₄.7H₂O,Na₂CO₃.10H₂O, Na₂CO₃.7H₂O, Na₃PO₄.12H₂O, Na₂HPO₄.12H₂O, Na₄P₂O₇.10H₂O,Na₂H₂P₂O₇.6H₂O, NaBO₃.4H₂O, Na₂B₄O₇.10H₂O, NaClO₄.5H₂O, Na₂SO₃.7H₂O,Na₂S₂O₃.5H₂O, NaBr.2H₂O, Na₂S₂O₆.6H₂O, K₃PO₄.3H₂O etc, preferablysuitable alkaline earth metal salt hydrates are for example, MgCl₂.6H₂O,MgBr₂.6H₂O, MgSO₄.7H₂O, Mg(NO₃)₂.6H₂O, CaCl₂.6H₂O, CaBr₂.6H₂O,Ca(NO₃)₂.4H₂O, Sr(NO₃)₂.4H₂O, Sr(OH)₂.8H₂O, SrBr₂.6H₂O, SrCl₂.6H₂O,SrI₂.6H₂O, BaBr₂.2H₂O, BaCl₂.2H₂O, Ba(OH)₂.8H₂O, Ba(BrO₃)₂.H₂O,Ba(ClO₃)₂.H₂O etc. Suitable transition metal salt hydrates are forexample, CrK(SO₄)₂.12H₂O, MnSO₄.7H₂O, MnSO₄.5H₂O, MnSO₄.H₂O, FeBr₂.6H₂O,FeBre6H₂O, FeCl₂.4H₂O, FeCl₃.6H₂O, Fe(NO₃)₃.9H₂O, FeSO₄.7H₂O,Fe(NH₄)₂(SO₄)₂.6H₂O, FeNH₄(SO₄)₂.12H₂O, CoBr₂.6H₂O, CoCl₂.6H₂O,NiSO₄.6H₂O, NiSO₄.7H₂O, Cu(NO₃)₂.6H₂O, Cu(NO₃)₂.3H₂O, CuSO₄.5H₂O,Zn(NO₃)₂.6H₂O, ZnSO₄.6H₂O, ZnSO₄.7H₂O etc. Suitable aluminium salthydrates are for example Al₂(SO₄)₃.18H₂O, AlNH₄(SO₄)₂.12H₂O, AlBre6H₂O,AlBr₃.15H₂O, AlK(SO₄)₂.12H₂O, Al(NO₃)₃.9H₂O, AlCl₃.6H₂O etc. A suitablelanthanum salt hydrate is LaCl₃.7H₂O.

Suitable acid hydrates according to the invention are organic acidhydrates such as citric acid monohydrate etc.

A salt or acid hydrate is preferably reacted with another salt or acidhydrate, it can however also be reacted with any non-hydrated chemicalcompound as long as crystal water is deliberated in sufficient amountsto drive the endothermic reaction with respect to the entropycontribution.

Suitable non-hydrated chemical compounds according to the invention mayinclude acids, alcohols, organic compounds and non-hydrated salts. Theacids may be citric acid, fumaric acid, maleic acid, malonic acid,formic acid, acetic acid, glacial acetic acid etc. The alcohols may bemannitol, resorcinol etc. The organic compounds may be urea etc. Thenon-hydrated salts according to the present invention may be such asanhydrous alkali metal salts, anhydrous alkaline earth metal saltsanhydrous transition metal salts anhydrous aluminium salts and anhydroustin salts and anhydrous lead salt and anhydrous ammonium salts andanhydrous organic salts. Suitable anhydrous alkali metal salt hydratesare for example NaClO₃, NaCrO₄, NaNO₃, K₂S₂O₆, K₂SO₄, K₂S₂O₆, K₂S₂O₃,KBrO₃, KCl, KClO₃, KIO₃, K₂Cr₂O₇, KNO₃, KClO₄, KMnO₄, CsCl etc. Suitableanhydrous alkaline earth metal salts are for example CaCl₂, Ca(NO₃)₂,Ba(BrO₃)₂, SrCO₃, (NH₄)₂Ce(NO₃)₆ etc. Suitable anhydrous transitionmetal salts are for example NiSO4, Cu(NO3)2. Suitable anhydrousaluminium salts are Al₂(SO₄)₃ etc. Suitable anhydrous tin salts areSnI₂(s), SnI₄(g) etc. Suitable anhydrous lead salts are PbBr₂, Pb(NO₃)₂etc. Suitable ammonium salts are NH₄SCN, NH₄NO₃, NH₄Cl, (NH4)2Cr2O7 etc.Suitable anhydrous organic salts are for example urea acetate, ureaformate, urea nitrate and urea oxalate etc.

It is further contemplated that the anhydrous form of any hydrated saltor hydrated acid as listed above may be used as a non-hydrated chemicalcompound in a reaction according to the present invention.

A liquid reactant according to the present invention may be a liquidsalt such as PBr₃, SCl₂, SnCl₄, TiCl₄, VCl₄ or a liquid organic compoundsuch as CH₂Cl₂ etc.

The number of reactants participating in the reaction is at least two.Some embodiments may use three or more reactants.

One possible reaction according to the present invention is

-   -   Na₂SO₄.10H₂O(s)+CaCl₂.6H₂O(s)→2Na⁺(aq)+2Cl⁻(aq)+CaSO₄.2H₂O(s)+14H₂O(l)        ΔH=2*(−240 kJ/mol)+2*(−167 kJ/mol)+(−2023 kJ/mol)+14*(−286        kJ/mol)−((−4327 kJ/mol)+(−2608 kJ/mol))=94 kJ/mol        ΔS=2*(58 J/K*mol)+2*(57 J/K*mol)+(194 J/K*mol)+14*(70        J/K*mol)−((592 J/K*mol)+(365 J/K*mol))=2.361 kJ/K*mol

At room temperature (T=298 K)

ΔG=ΔH−T*ΔS=94 kJ/mol−298 K*0.447 kJ/K*mol=−39 kJ/mol

The negative sign indicates that the reaction is spontaneous.

The stoichiometric number of products to reactants is 19/2=9.5:1

Another possible reaction according to the present invention is

-   -   Na₂SO₄.10H₂O(s)+Ba(OH)₂.8H₂O(s)→BaSO₄(s)+2Na⁺(aq)+2OH⁻(aq)+18H₂O(l)

ΔH=−1473 kJ/mol+2*(−240 kJ/mol)+2*(−230 kJ/mol)+18*(−286 kJ/mol)−(−4327kJ/mol+(−3342 kJ/mol))=108 kJ/mol

ΔG at room temperature (T=298 K) for this reaction can be directlycalculated:

ΔG=−1362 kJ/mol+2*(−262 kJ/mol)+2*(−157 kJ/mol)+18*(−237 kJ/mol)−(−3647kJ/mol+(−2793 kJ/mol))=−26 kJ/mol

Thus this reaction is spontaneous. The stoichiometric number of productsto reactants is 23/2=11.5:1

A further possible reaction according to the present invention is

-   -   Ba(OH)₂.8H₂O(s)+2NH₄SCN(s)→Ba(SCN)₂+2NH₃(g)+10H₂O(l)        ΔH=102 kJ/mol        ΔS=0.495 kJ/K*mol        ΔG=ΔH−T*ΔS=102 kJ/mol−298 K*0.495 kJ/K*mol=−45.5 kJ/mol

The reaction is spontaneous. The stoichiometric number of products toreactants is 13/3=4.33:1

Examples of further reactions are

a) Ba(OH)₂.8H₂O(s)+2NH₄NO₃(s)→Ba(NO₃)₂+2NH₃(g)+10H₂O(l)b) Ba(OH)₂.8H₂O(s)+2NH₄Cl(s)→BaCl₂+2NH₃(g)+10H₂O(l)

Additives and Activators

The reaction is preferably activated by the addition of a polar solvent,such as water, glycerin, ethanol, propylene glycol, etc but the reactionmay also be activated simply by contacting the reactants.

In some reactions the reactants may be non-reactive when contacted orbeing mixed. For these reactions a suitable catalyst may be used toenable the reaction.

In some embodiments the solid reactants are coated or microencapsulated.Suitable external coatings are heat resistant but dissolvable uponcontact with an activation fluid capable of dissolving the coating.Suitable coatings include carbohydrates such as starch and cellulose,polyethers such as polyethylene glycol (PEG) but also shellac orplastics. Suitable activation fluids include water alcohols, organicsolvents, acids. As an alternative to a coating, the solid reactants maybe embedded in a soluble gel or foam.

By use of a coating the reactants can be premixed in order to increasethe reaction rate. Furthermore, coating of reactants prevents prematureactivation of the cooling effect due to storage conditions or heattreatment of the beverage. In some embodiments a part of the reactantmass is coated with a thicker coating in order to slow down the reactionand prolong the cooling provided by the reaction. In other embodimentsmore than one coating may be applied to the reactants or differentcoatings may be applied to different reactants or parts of the reactantmass. Instead of a coating the reactants can be suspended in anon-aqueous fluid such as an organic solvent.

A retardation temperature setting agent having a suitable meltingtemperature may be used with the current invention. A suitable meltingtemperature may be such a temperature that the retardation temperaturesetting agent is liquid at temperatures above a freezing point or anydesirable temperature yielding a desired cooling of the beverage to becooled and solidifies as the temperature descends below this point thusretarding the reaction in order to prevent freezing of the beverage inthe beverage container. The retardation temperature setting agent may beany chemical compound with a suitable melting temperature above thefreezing temperature of water such as a temperature between 0° C. to+10° C. such as 2° C. to 6° C. such that the solidified form of theretardation temperature setting agent decreases the reaction rate of thereaction according to the present invention. Examples of suitableretardation temperature setting agents include polyethylene glycol, afatty acid, or a polymer.

The reactants can be in the form of granulates of varying sizes totailor the reaction rate to the specific application. The granules mayalso be coated as described above.

For some reactions it is preferable to add a solvent such as glycerol ora trace contaminant to prevent the formation of crystals of a productfrom coating remaining reactants thus inhibiting further reaction. Anadsorbent can be used to selectively adsorb a product in order tocontrol the reaction rate and/or ensure complete reaction. For somereactions the liquid activator used to initiate the reaction may alsoserve as a selective adsorption-controlling agent to control thereaction.

In reactions producing acidic or basic products a pH-regulating buffermay be included. The buffer may also be used to promote the dissolutionof products in form of gas.

It is contemplated that one or more reactants may be formed in situ fromprecursors. This can be advantageous for preventing premature activationor preactivation of the cooling device after it has been placed in thecontainer.

It is further contemplated that the following additives may be relevantfor some reactions in the context of controlling the reaction:3,7-diamino-5-phenothiazinium acetate, 18 crown 6 ether,1,3-dimethyl-2-imidazolidinone.

Presently Preferred Reaction

The presently preferred reaction is a reaction between strontiumhydroxide octahydrate and ammonium nitrate. To make the end productsafe, magnesium nitrate hexahydrate is added as a third reactant. Mostpreferably, the magnesium nitrate hexahydrate is used as a coating forseparating the strontium hydroxide octahydrate and ammonium nitrate. Theabove reactants react in a primary reaction and a NH₃ pacificationreaction. The primary reaction having a high cooling efficiency is asfollows:

3Sr(OH)₂.8H₂O(s)+6NH₄NO₃(s)→3Sr²⁺+6NO₃ ⁻+6NH₃+30H₂O

Since NH₃ may be considered as toxic, or at least not pleasantlysmelling, it has to be pacified by a further reaction. The NH₃pacification reaction has a cooling efficiency which is lower than thecooling efficiency of the primary reaction:

3Sr²⁺+6NO₃ ⁻+6NH₃+30H₂O+Mg(NO₃)₂.6H₂O(s) 3Sr²⁺+8NO₃ ⁻+Mg(NH₃)₆ ²⁺+36H₂O

The end product is a white gel that smells slightly of ammonia and whichis completely safe.

88 ml of the above reactants are required to cool down 330 ml ofbeverage by 20 degrees centigrade. Thus, a common 440 ml beverage canmay be used for accommodating 330 ml of beverage and 88 ml of reactants.

Cooling of Beverage

Dependent on the reaction used, the heat capacity of the reactionmixture and the beverage, the initial temperature of the beverage andthe amounts of beverage and reactants, respectively, a wide range ofcooling effects may be obtained.

A cooling device according to the present invention may contain anyamount of reactant as long as the volume of the cooling device does notexceed 30% of the container volume.

The cooling effect of the cooling device in the beverage containershould be sufficient to cool a volume of beverage at least 10° C. withina period of time of no more than 5 min., preferably no more than 2 min.

For a beverage consisting mainly of water the specific heat capacity canbe approximated with the specific heat capacity for liquid water: 4.18kJ/kg. K. The cooling effect q needed for cooling the beverage is givenby the equation: q=m·ΔT·Cp. Thus in order to cool 1 kg of beverage 20°C. the cooling device must absorb 83.6 kJ of heat from the beverage tobe cooled. Thus in the present invention a heat reduction of thebeverage should be at least 50 Joules/ml beverage, preferably at least70 Joules/ml beverage such as 70-85 Joules/ml beverage preferablyapproximately 80-85 Joules/ml beverage within a time period of no morethan 5 min, preferably no more than 3 min, more preferably no more than2 min.

According to further embodiments, the container body may comprise abeverage keg of polymeric or metallic material having a volume of 3-50liters, the keg being either collapsible or rigid, and the closure beinga keg coupling. Alternatively, the container body may comprise a bottleof glass or polymeric material, the bottle having a volume of 0.2-3liters, and the closure being a screw cap, crown cap or stopper. Yetalternatively, the container body may comprise a beverage can and abeverage lid of metallic material, preferably aluminum or an aluminumalloy, the can having a volume of 0.2-1 liters, and the closure beingconstituted by an embossing area of the beverage lid. Yet alternatively,the container may comprise a bag, preferably as a bag-in-box, bag-in-bagor bag-in-keg.

According to further embodiments, the container comprises guidingelements for guiding the flow of beverage from the container body. Theguiding elements may serve to guide the flow of the beverage via thecooling device towards the closure. The cooling device may be locatedwithin the container, or alternatively the cooling device is locatedoutside the container. The container body may constitute a double walledcontainer constituting an inner wall and an outer wall, and the coolingdevice may be located between the inner and outer wall.

According to further embodiments, the container may comprise a pressuregenerating device either accommodated within the container or connectedto the container via a pressurization hose. The pressure generatingdevice preferably comprises a carbon dioxide generating device forpressurization of the beverage in the beverage container.

According to further embodiments, the container may comprise a tappingline and a tapping valve for selectively dispensing beverage from thebeverage container. The beverage container may be filled with carbonatedbeverage such as beer, cider, soft drink, mineral water, sparkling wine,or alternatively non-carbonated beverage such as fruit juice, milkproducts such as milk and yoghurt, tap water, wine, liquor, ice tea, oryet alternatively a beverage constituting a mixed drink.

According to further embodiments, the cooling device forms an integralpart of the beverage container or a part of the top of the beveragecontainer, alternatively a part of the wall or bottom of the beveragecontainer. The cooling device is fastened onto the base of the beveragecontainer, alternatively the wall of the container, yet alternativelythe top of the container, or alternatively the cooling deviceconstitutes a widget, which is freely movable within the container.

According to a further embodiment, the cooling device may be configuredas a metal can of the size of a beverage can, or configured as a coolingbox for receiving a number of beverage containing containers, orconfigured as a cooling stick to be positioned in a beverage bottle orthe like, or configured as a sleeve to be positioned encircling a partof a container, e.g. the neck of a bottle or the body part of a metalcan or bottle or configured as a part of the closure or cap of a bottle.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention and its many advantages will be described in more detailbelow with reference to the accompanying schematic drawings, which forthe purpose of illustration show some non-limiting embodiments and inwhich:

FIGS. 1 a and 1 b illustrate a self-cooling beverage container having acooling device having a gas permeable membrane in a pre-activated stateand an activated state, respectively.

FIG. 1 c illustrates a close-up view of the self-cooling beveragecontainer in the activated state as shown in FIG. 1 b.

FIGS. 2 a and 2 b illustrate a self-cooling container having a coolingdevice with an auxiliary reactant chamber in the pre-activated andactivated states, respectively.

FIG. 3 a illustrates a self-cooling container having a cooling devicewith a soluble plug.

FIGS. 3 b and 3 c illustrate the self-cooling container having a coolingdevice with a soluble plug of FIG. 3 a in the pre-activated andactivated states, respectively.

FIGS. 4 a and 4 b illustrate a self-cooling container having a coolingdevice with a piercable membrane in the pre-activated and activatedstates, respectively.

FIGS. 5 a and 5 b illustrate a self-cooling beverage container having acooling device with a cap in the pre-activated and activated states,respectively.

FIGS. 6 a and 6 b illustrate a self-cooling beverage container having acooling device with a rupturable diaphragm in the pre-activated andactivated states, respectively.

FIGS. 7 a and 7 b illustrate a self-cooling beverage container having acooling device with a telescoping valve in the pre-activated andactivated states, respectively.

FIGS. 8 a and 8 b illustrate a self-cooling beverage container having acooling device with a water-soluble diaphragm in the pre-activated andactivated states, respectively.

FIGS. 9 a and 9 b illustrate a self-cooling beverage container having acooling device with a flexible cylinder in the pre-activated andactivated states, respectively.

FIG. 9 c illustrates the self-cooling beverage container of FIG. 9 afurther comprising a gripping member.

FIGS. 9 d and 9 e show close-up views of the gripping member of FIG. 9 cin the pre-activated and activated states; respectively.

FIGS. 10 a and 10 b illustrate a self-cooling beverage container havinga cooling device with a pair of caps in the pre-activated and activatedstates, respectively.

FIGS. 11 a and 11 b illustrate a self-cooling beverage container havinga cooling device with a cap and a rupturable diaphragm in thepre-activated and activated states, respectively.

FIGS. 12 a and 12 b illustrate a self-cooling beverage container havinga cooling device with a piercable membrane and a rupturable membrane inthe pre-activated and activated states, respectively.

FIGS. 13 a and 13 b illustrate a self-cooling beverage container havinga cooling device constituting a widget in the pre-activated andactivated states, respectively.

FIGS. 14 a and 14 b illustrate a self-cooling beverage container havinga cooling device constituting a widget and an action control fluid inthe pre-activated and activated states, respectively.

FIGS. 15 a and 15 b illustrate a self-cooling beverage container havinga cooling device constituting a widget having an additional reactantchamber in the pre-activated and activated states, respectively.

FIG. 16 a shows a cooling box having a rectangular shape and including acooling device having a can shape in an unassembled state.

FIG. 16 b shows a top view of the cooling box of FIG. 16 a in anassembled state;

FIG. 17 a shows a cooling box having a round shape including a centrallylocated cooling device in the unassembled state.

FIGS. 17 b and 17 c show a perspective view and a top view,respectively, of the cooling box of FIG. 17 a.

FIGS. 18 a-f show the filling process of a self-cooling beveragecontainer having a cooling device mounted in the container.

FIGS. 19 a-f show the filling process of a self-cooling beveragecontainer having a cooling device constituting a widget.

FIGS. 20 a-f show a filling process of a self-cooling beverage containerhaving a lid mounted cooling device.

FIGS. 21 a and 21 b show a self-cooling party keg system in thepre-activated and activated states, respectively.

FIGS. 22 a and 22 b show a beverage dispensing system having a keg witha cooling device for achieving instant cooling in the pre-activated andactivated states, respectively.

FIGS. 23 a and 23 b show a beverage dispensing system having a beveragekeg having a cooling device with a piercable membrane in thepre-activated and activated states, respectively.

FIG. 24 shows a beverage bottle having a button activatable coolingdevice.

FIG. 25 shows a beverage bottle having a pressure activated coolingdevice.

FIGS. 26 a and 26 b show a beverage bottle having a cap mounted coolingdevice, which is activated by the user in the pre-activated andactivated states, respectively.

FIGS. 27 a and 27 b show a cooling device constituting a drink stickwith an internal cooling device in the pre-activated and activatedstates, respectively.

FIG. 27 c shows the drink stick of the cooling device of FIG. 27 b afteractivation.

FIG. 27 d shows the drink stick of FIG. 27 c inserted into a bottle.

FIGS. 28 a and 28 b show a bottle sleeve to be mounted on the neck of abeverage bottle.

FIG. 28 c is a perspective view of the bottle sleeve of FIGS. 28 a and28 b mounted on the neck of the beverage bottle.

FIGS. 29 a and 29 b show a bottle sleeve to be mounted around the bodyof the beverage bottle in the pre-activated and activated states,respectively.

FIG. 29 c is a perspective view of the bottle sleeve of FIGS. 29 a and29 b.

FIG. 29 d shows the bottle sleeve of FIG. 29 c being attached to thebeverage bottle.

FIG. 30 shows a reaction crystal having a selective adsorbant inhibitinggrowth at the corners.

FIG. 31 is a dispensing and refrigerator system for accommodating aplurality of beverage cans.

FIG. 32 is a refrigerator system for accommodating a plurality ofbeverage cans.

The figures illustrate numerous exemplary embodiments of a coolingdevice according to the present invention.

DETAILED DESCRIPTION

FIG. 1 a shows a partial intersected view of a self-cooling container 10^(I) according to the present invention. The self-cooling container 10^(I) comprises a beverage can 12 made of thin metal sheet of e.g.aluminium or an aluminium alloy. The beverage can 12 has a cylindricalbody, which is closed off by a beverage can base 14 and a lid 16. Thelid 16 comprises a tab 18 (FIG. 1 b) and an embossed area constituting aclosure. (The tab and the embossed area are not visible in the presentview.) The beverage can 12 includes a cooling device 20 ^(I), which islocated juxtaposed to the beverage can base 14 inside the beverage can12. The cooling device 20 ^(I) comprises a cylinder of thin metal sheetsimilar to the beverage can 12, however significantly smaller in size.Alternatively, the cooling device 20 ^(I) may constitute a laminatebeing made of plastic or similar polymeric material coated with thinaluminium foil. The size of the cooling device 20 ^(I) corresponds toabout 20% to 30% of the total volume of the beverage can 12, preferablyabout 25% of the volume of the beverage can 12, for achieving asufficient cooling efficiency while not substantially reducing theamount of beverage which may be accommodated inside the beverage can 12.A beverage, preferably a carbonated beverage such as beer, sparklingwine or various soft drinks, is filled into the beverage can 12 andaccommodates typically 70% of the volume of the beverage can 12 allowingfor about 5% space between the lid 16 and the upper surface of thebeverage. The cooling device 20 ^(I) extends between a bottom 22 and atop 24. The bottom 22 is preferably fixated to the beverage can base 14so that the cooling device 20 ^(I) assumes a stable position inside thebeverage can 12. Alternatively, the cooling device 20 ^(I) constitutesan inherent part of the beverage can 12. For example, the beverage can12 including the cooling device 20 ^(I) may be stamped out of metalsheet in one piece. The top 24 of the cooling device 20 ^(I) as well asthe lid 16 of the beverage can 12 constitutes separate parts, which areapplied after the respective cooling device 20 ^(I) and the beverage can12 have been filled. The top 24 of the cooling device 20 ^(I) seals offthe interior of the cooling device 20 ^(I) such that no beverage mayenter. The top 24 comprises a gas permeable membrane 26, which allowsgases such as air or carbon dioxide, but prevents liquid, such asbeverage, to enter the interior of the cooling device 20 ^(I). Theinterior of the cooling device 20 ^(I) is divided into a pressure space32 located adjacent to the gas permeable membrane 26, a main reactantchamber 28 located near the bottom 22 and a water chamber 44 locatedbetween the pressure space 32 and the main reactant chamber 28. The mainreactant chamber 28 constitutes a greater part of the cooling device 20^(I) and is filled with granulated reactants 29. The granulatedreactants 29 comprises at least two separate reactants which whenreacting with each other will draw energy from the surrounding beverageand thereby cause a cooling of the beverage. The reaction will typicallybe initiated when the two reactants contact each other. The exactcompositions of the reactants will be described in detail later in thechemistry part of the present description. At least one of the compoundsconstitutes a granulate having a water-soluble coating, which preventsthe reactants from contacting each other and thus prevents any reactionto start. The water soluble coating may be e.g. starch. In analternative embodiment the granulate or the granulates may be preventedfrom reacting by being embedded in a soluble gel or foam. Furtheralternatively, the reactants may be provided as shallow, highlycompacted discs or plates separated from one another through the abovementioned coating, gel or foam.

The pressure space 32 is separated from the water chamber 44 by aflexible diaphragm 30. The flexible diaphragm 30 has a funnel shape andextends from a rounded circumferential reinforcement bead 34constituting the periphery of the flexible diaphragm 30 to a circularwall 40 constituting the centre of the flexible diaphragm 30. Thecircular wall 40 separates the pressure space 32 from the main reactantchamber 28. The rounded circumferential reinforcement bead 34 ispositioned juxtaposed to a washer 36, which seals the roundedcircumferential reinforcement bead to the top 24. The water chamber 44is separated from the main reactant chamber 28 by a rigid cup-shapedwall 38 extending from the top 24 inwards and downwards. The flexiblediaphragm 30 comprises a circumferential gripping flange 42 extendingdownwards at the circular wall 40. The circumferential gripping flange42 grips around the end of the cup-shaped wall 38, thus sealing thewater chamber 44 from the main reactant chamber 28.

The cooling device 20 ^(I) is prepared by filling the main reactantchamber 28 with the granulate reactants 29 and filling the water chamber44 with water, then the top 24 is attached and sealed to the coolingdevice 20 ^(I). Subsequently, the beverage can 12 is filled withbeverage, pressurised and sealed by the lid 16. The pressure in thebeverage can 12 ensures that the cooling device 20 ^(I) is notactivated, since equal pressure is maintained inside the beverage can 12and inside the cooling device 20 ^(I).

FIG. 1 b shows a partial intersected view of a self-cooling container 10^(I) when the beverage can 12 has been opened and the chemical reactionin the cooling device 20 ^(I) has been activated. The beverage can 12 isopened by operating the tab 18 from its normal horizontal positionjuxtaposed the lid 16 to a vertical position extending outwardly inrelation to the lid 16. By operating the tab 18 to the verticalposition, the tab 18 will protrude into the embossing in the lid 16causing the embossing to rupture and define a beverage outlet (notshown) in the beverage can 12. When the beverage can 12 has been opened,the high pressurized CO₂ gas inside the beverage can 12 will escape tothe outside atmosphere. The atmospheric pressure in the beverage can 12will cause gas to slowly escape from the pressure space 32 through thegas permeable membrane 26 to the beverage can 12. At the same time, thehigh pressure inside the main reactant chamber 28 will apply a pressureonto the flexible diaphragm 30, thereby causing the flexible diaphragm30 to move towards the top 24. The rounded circumferential reinforcementbead 34 and the washer 36 will seal the pressure space 32 and the mainreactant chamber 28 fluid tight. When the flexible diaphragm 30 hasassumed the activated position, i.e. moved towards the top 24, thecircumferential gripping flange 42 will detach from the rigid cup-shapedwall 38 and allow the water contained in the water chamber 44 to flowinto the main reactant chamber 28. The water entering the main reactantchamber will dissolve the water soluble coating of the reactantgranulates and thereby cause the chemical reaction to start. Thereaction is an endothermic reaction, which will draw energy from thebeverage, i.e. the beverage will become colder while thermal energyflows from the beverage to the cooling device 20 ^(I). More details onthe chemical reaction will follow later in the description. The thermalenergy drawn by the cooling device 20 ^(I) will chill the beverage inthe beverage can 12. After a few seconds, the relative temperature ofthe beverage will fall about ten degrees C.°, typically twenty degreesC.°, and the beverage consumer may enjoy a chilled beverage shortlyafter opening the beverage can 12. A beverage can 12 stored withoutrefrigeration in a store may typically have a temperature of about 22degrees C. After opening, the beverage quickly cools down to about 6degrees C., counting for thermal losses etc. The time needed for thechilling typically is less than 5 minutes, more typically 3 minutes.When the beverage consumer has finished drinking the beverage, thebeverage can 12 may be disposed and the metal in the beverage can 12 maybe recycled in an environmentally friendly way.

FIG. 1 c shows a partial intersected view of an alternative embodimentof a self-cooling container 10 ^(I) shortly after the beverage can 12has been opened and the chemical reaction in the cooling device 20 ^(I)has been activated, similar to FIG. 1 b. FIG. 1 c additionally shows afirst close-up view showing the upper part of the reactant chamber 28and a second close up view showing the lower part of the reactantchamber 28. From the close up views it can be seen that at the presenttime the water, designated by dashed lines in FIG. 1 c, has contactedthe granulated reactants 29 of the upper part of reactant chamber 28,whereas the lower part of the reactant chamber 28 remains dry.

The granulate reactants 29 have a core and a coating which is completelycovering the core. The granulate reactants 29 are divided up in twotypes: one type granulate reactants 29 has a coating of a first reactantdesignated 29A and a core of a second reactant designated 29B, andanother type granulate reactants 29 has a coating of the first reactantdesignated 29A and a core of a third reactant designated 29C.

In the second close-up view showing the lower part of the reactantchamber 28 the chemical reaction cannot initiate, since the cores 29Band 29C cannot interact with each other. In the first close-up viewshowing the upper part of the reactant chamber 28 the granulatereactants 29 are subjected to water, and the coating 29 c begins todeteriorate causing all three reactants 29ABC to mix and react with eachother.

The reactant B and C may initially react and produce a reaction productwhich is pacified by reacting with reactant A.

FIG. 2 a shows a partial intersected view of a further embodiment of aself-cooling container 10 ^(II) comprising all of the features of theself-cooling container 10 ^(I) of FIGS. 1 a and 1 b. The self-coolingcontainer 10 ^(II) of the present embodiment, however, further comprisesan auxiliary cup-shaped wall 46 mounted outside and below the maincup-shaped wall 38. An auxiliary gripping flange 48 constituting anelongation of the main gripping flange 42 together with an auxiliarycup-shaped wall 46 and a main cup-shaped wall 38 define an auxiliaryreactant chamber 50. The auxiliary reactant chamber 50 is filled with anauxiliary reactant granulate 29, which constitutes one of the reactantsof the reaction. The other reactant 29′ is located in the main reactantchamber 28, thereby eliminating the need of a coating of the reactantgranulates.

FIG. 2 b shows the self-cooling container 10 ^(II) of FIG. 2 a when thebeverage can 12 has been opened and the chemical reaction has beenactivated. In the activated state, the circumferential gripping flange42 has detached from the cup-shaped wall 38 as shown in FIG. 1 a,thereby allowing the water in the water chamber 44 to flow into the mainreactant chamber 28. At the same time, the auxiliary gripping flange 48,which is connected to the flexible diaphragm 30 via the circumferentialgripping flange 42 will detach from the auxiliary cup-shaped wall 46 andallow the auxiliary reactant 29 to enter the main reactant chamber 28,thereby activating the chemical reaction. The present embodimentrequires an additional chamber but has the benefit of not requiring anycoating of the reactant granulates, since the reactants are stored inseparate chambers.

FIG. 3 a shows a cooling device 20 ^(III) for use in a self-coolingcontainer 10 ^(III) (FIGS. 3 b and 3 c) similar to the self-coolingcontainer 10 ^(II) shown in FIGS. 2 a and 2 b. The self-coolingcontainer 10 ^(III) has a pressure space 32, however, instead of a gaspermeable membrane, a water-soluble plug 26′ is accommodated in the top24 of the cooling device 20 ^(III). The water-soluble plug 26′ may be ofany water-soluble material, which is non-toxic and may form a pressureproof plug of sufficient rigidity, which dissolves within a few minuteswhen subjected to an aqueous solution such as beverage. It iscontemplated that non-toxic implies that the material being allowed forusage in consumables by e.g. a national health authority or the like.Such materials may include sugar, starch or gelatine. The soluble plug26′ allows the cooling device 20 ^(III) to be prepared and pressurisedan extended time period such as days or weeks before being used in abeverage can. The soluble plug 26′ prevents the pressure inside thecooling device 20 ^(III) i.e. inside the main reactant chamber 28, thewater chamber 44 and the pressure space 32 to escape to the outsidethrough the top 24. The flexible membrane 30 is in the presentembodiment made of rubber and comprises a support diaphragm 31 as wellmade of rubber and which is located juxtaposed to the cup-shaped wall 38and extending between the circular wall 40 and the roundedcircumferential reinforcement bead 34. To equalize the pressure betweenthe flexible membrane 30 and the support diaphragm 31, a pressure inlet52 is located on the flexible membrane to allow the pressure to equalisebetween the pressure space 32 and the space between the supportdiaphragm 31 and the flexible membrane 30.

FIG. 3 b shows the self-cooling container 10 ^(III) comprising abeverage can 12 and the cooling device 20 ^(III) located inside thebeverage can 12 before the chemical reaction has been activated. Thesoluble plug 26′ will prevent the pressure inside the pressure space 32to escape to the outside of the cooling device20 ^(III), while thebeverage can 12 is filled with beverage and carbonated/pressurised.After a certain time period or alternatively during pasteurisation, thesoluble plug 26′ is dissolved and fluid communication is allowed betweenthe interior of the beverage can 12 and the pressure space 32 of thecooling device20 ^(III). The pressure inside the beverage can 12 keepsthe cooling device 20 ^(III) in its pre-activated state, i.e. thechemical reaction is not started.

FIG. 3 c shows the self-cooling container 10 ^(III) according to FIG. 3b when the beverage can 12 has been opened and the chemical reaction hasbeen activated. When the beverage can 12 has been opened, the pressureinside the beverage can 12, as well as inside the pressure space 32,falls to the ambient pressure outside the beverage can 12. This causesthe chemical reaction in the cooling device 20 ^(III) to activate aspreviously described in connection with FIGS. 2 a and 2 b.

FIG. 4 a shows a further embodiment of a self-cooling container 10^(Iv). The self-cooling container 10 ^(IV) comprises a beverage can 12′similar to the beverage can described in connection with FIGS. 1 a and 1b to 3 b and 3 c. The beverage can 12′ has a beverage can base14, a lid16 and a cooling device20 ^(IV), which is fixated onto the lid 16 andextending into the beverage can 12′. The cooling device 20 ^(IV)comprises a cylindrical aluminium tube extending towards the beveragecan base 14. A pressure inlet 52 is defined in the lid 16 for allowingfluid communication between the outside atmospheric pressure and apressure space 32′, which is defined inside the cooling device 20 ^(IV)between the lid 16 and a diaphragm 30′. The diaphragm 30′ is made of aflexible material such as rubber and forms a fluid tight barrier betweenthe pressure space 32′ and a water chamber 44′. The water chamber 44′ isseparated from a main reactant chamber 28′ by a rupturable diaphragm 54.The rupturable diaphragm 54 is made of a flexible material similar tothe diaphragm 30′. The rupturable diaphragm 54 may be ruptured, i.e.irreversibly opened by a piercing element 56 constituting a needle,which is located inside the main reactant chamber 28′ and pointingtowards the rupturable diaphragm 54. The main reactant chamber 28′ isfilled with a coated granulate reactant similar to the embodimentsdescribed in connection with FIGS. 1 a-c to 3 a-c. The main reactantchamber 28′ is separated from the beverage can 12′ by a bottom 22′ whichis located near, however not contacting, the beverage can base14. Thebottom 22′ is made of the same material as the outer wall of the coolingdevice20 ^(IV), i.e. preferably aluminium. The bottom 22′ is connectedto the outer wall of the cooling device 20 ^(IV) via a corrugation 58allowing the bottom 22′ to be flexible and bistable, i.e. able to adoptmechanically stable inward and outward bulging states, respectively.When the beverage can 12′ is filled and pressurised, the pressure insidethe beverage can 12′ will cause the bottom 22′, the rupturable diaphragm54 and the diaphragm 30′ to bulge in an inward direction.

FIG. 4 b shows the self-cooling container 10 ^(IV) comprising thebeverage can 12′, which has been opened by operating the tab 18. Byoperating the tab 18, an embossing in the lid 16 is ruptured and anopening is formed in the lid 16 allowing the beverage to be poured outand the pressure to escape. When the pressure escapes, the bottom 22′ ofthe cooling device 20 ^(IV) will bulge towards the beverage can base 14due to the internal pressure in the cooling device 20 ^(I). The bottom22′ is made bistable, so that when bulging towards the beverage can base14, a subatmospheric pressure results in the main reactant chamber 28′and causes the rupturable diaphragm 54 and the diaphragm 30′ to bulgetowards the beverage can base 14. The rupturable diaphragm 54 willtherefore bulge into the piercing element 56 causing the rupturablediaphragm 54 to burst. The rupturable diaphragm 54 may be a burstingdiaphragm or alternatively have a predetermined breaking point oralternatively have a built-in tension so that when the piercing element56 enters the rupturable diaphragm 54, an opening is created between thewater chamber 44′ and the main reactant chamber 28′ causing the water inthe water chamber 44′ to enter the main reactant chamber 28′, therebyactivating the chemical reaction resulting in a cooling of the beverage.The chemical reaction will draw energy from the surrounding verge andthereby cause a relative cooling of at least 10 degrees C.°, preferably20 degrees C.° or more.

FIG. 5 a shows a self-cooling container 10 ^(V), similar to theself-cooling container 10 ^(IV) of FIGS. 4 a-b. Instead of a rupturablediaphragm, the self-cooling container 10 ^(V) has a main cap 60 made ofplastic material separating the water chamber 44′ and the main reactantchamber 28′. The main cap 60 is held in place by a main cap seat 62constituting an inwardly protruding flange which is fixed to the innerwall of the cooling device 20 ^(V) and which applies a light pressureonto the main cap 60. The main cap 60 constitutes a shallow circularplastic element forming a fluid tight connection between the waterchamber 44′ and the main reactant chamber 28′.

FIG. 5 b shows the self-cooling container 10 ^(V) according to FIG. 5 a,which has been opened and activated similar to the beverage candescribed in FIG. 4 b. When the beverage can 12′ has been opened, thebottom 22′ of the cooling device 20 ^(V) will bulge towards the beveragecan base 14, which will cause a pressure drop inside the main reactantchamber 28′ resulting in the main cap 60 being ejected from the main capseat 62 and falling into the main reactant chamber 28′, thereby allowingfluid communication between the water chamber 44′ and the main reactantchamber 28′. Water will therefore flow from the water chamber 44 intothe main reactant chamber 28′, thereby activating the chemical reactionand causing the beverage to be cooled. As the granulate reactant isbeing dissolved, the main cap 60 may fall towards the bottom 22′ of thecooling device 20 ^(V).

FIG. 6 a shows a self-cooling container 10 ^(VI) similar to theself-cooling container 10 ^(V) shown in FIGS. 5 a-b, however, instead ofa main cap seat and a main cap, the present embodiment comprises asupport mesh 66 and a rupturable diaphragm 54′ separating the waterchamber 44′ and the main reactant chamber 28′. The support mesh 66constitutes a grid made of metal or plastics, which is placed in ajuxtaposed position in relation to a rupturable diaphragm 54′, where thediaphragm 54′ is facing the main reactant chamber 28′ and the supportmesh 66 is facing the water chamber 44′. The rupturable diaphragm 54′constitutes a burst membrane, which prevents fluid communication betweenthe water chamber 44′ and the main reactant chamber 28′. The supportmesh 66 prevents the rupturable diaphragm 54′ from bulging upwardlytowards the pressure inlet 52′ and rupturing in case the pressure in themain reactant chamber 28′ exceeds the pressure in the water chamber 44′.

FIG. 6 b shows a self-cooling container 10 ^(VI) when the beverage can12′ has been opened. By opening the beverage can 12′, the pressure isreduced inside the beverage can 12′ causing the bottom 22′ to bulgetowards the beverage can base 14, thereby reducing the pressure insidethe main reactant chamber 28′. The reduced pressure inside the mainreactant chamber 28′ causes the rupturable diaphragm 54′ to bulgetowards the beverage can base 14. The rupturable diaphragm 54′ is aburst membrane, which is caused to rupture without use of a piercingelement. The rupturable diaphragm 54′ may constitute a non resilientmembrane which is caused to burst by the pressure difference between themain reactant chamber 28′ and the water chamber 44′, therebyestablishing a fluid communication between the water chamber 54′ and themain reactant chamber 28′. The water entering the main reactant chamber28′ from the water chamber 44′ will activate the chemical reactioncausing a cooling effect on the surrounding beverage as describedpreviously in the FIGS. 4 a-b to 5 a-b.

FIGS. 7 a and 7 b show a self-cooling container 10 ^(VII) similar to theself-cooling container 10 ^(VI) of FIGS. 6 a-b, however, instead of arupturable diaphragm and a piercing element, a telescoping valve 68 isseparating the water chamber 44′ and the main reactant chamber 28′. Thetelescoping valve 68 constitutes a plurality of valve elements 69, 70and 71. The valve elements 69, 70 and 71 constitute circular cylindricalflange elements. The first valve element 69 having the largest diameteris fixated to the inner wall of the cooling device 20 ^(VII). The firstvalve element 69 is protruding slightly towards the bottom 22′ of thecooling device 20 ^(VII) and constitutes an inwardly protruding bead.The second valve element 70 constitutes a flange element having an upperoutwardly protruding bead sealing against the first valve element 69 andan inwardly protruding bead sealing against the outwardly protrudingbead of the first valve element 69. The third valve element 71constitutes a cup-shaped element having an upper outwardly protrudingbead sealing against the outwardly protruding bead of the second valveelement 70 and a lower horizontal surface sealing against the lowerinwardly protruding bead of the second valve element 70.

FIG. 7 b shows the self-cooling container 10 ^(VII) of FIG. 7 a when thebeverage can 12′ has been opened. As previously described in FIG. 6 b,the opening of the beverage can 12′ causes the bottom 22′ of the coolingdevice 20 ^(VII) to bulge outwardly, thereby causing the pressure in themain reactant chamber 28′ to be reduced, thereby causing the second andthird valve elements 70 and 71 to move in a direction towards the bottom22′ of the cooling device 20 ^(VII) so that the outwardly protrudingbead of the second valve element 70 seals against the inwardlyprotruding bead of the first valve element 69 and the outwardlyprotruding bead of the third valve element 71 seals against the inwardlyprotruding bead of the second valve element 70. The second and thirdvalve elements 70 and 71 are provided with circumferentially distributedvalve apertures 72, which allow fluid communication between the waterchamber 44′ and the main reactant chamber 28′. Thus, water is allowed toflow from the water chamber 44′ to the main reactant chamber 28′.

FIG. 8 a shows a self-cooling container 10 ^(VIII) similar to theself-cooling container 10 ^(IV) described in connection with FIGS. 4a-b, however, an auxiliary reactant chamber 50′ is provided between thewater chamber 44′ and the main reactant chamber 28′. The water chamber44′ is separated from the auxiliary reactant chamber 50′ by a support 74and a rupturable diaphragm 54″. The support 74 seals between the innerwall of the cooling device 20 ^(VIII) and the rupturable diaphragm 54″,which is centrally located and covering a descending pipe 76, which isprotruding towards the main reactant chamber 28′. The auxiliary reactantchamber 50′ and the main reactant chamber 28′ are separated by a watersoluble diaphragm 78.

FIG. 8 b shows the self-cooling container 10 ^(VIII) as described inFIG. 8 a when the beverage can 12′ has been opened. The opening of thebeverage can causes the bottom 22′ of the cooling device 20 ^(VIII) tobulge outwardly as described above in connection with FIGS. 4 a-b toFIGS. 7 a-b. The reduced pressure in the main reactant chamber 28′causes the water soluble diaphragm 78 to bulge towards the bottom 22′and the resulting low pressure in the auxiliary reactant chamber 50′causes the rupturable diaphragm 54″ to burst and allowing the water inthe water chamber 44′ to enter the descending pipe 76 and flow towardsthe water soluble diaphragm 78. When the water soluble diaphragm 78 isdissolved by the water from the descending pipe, the auxiliary reactants29, constituting the first of the two reactants required for thechemical reaction to activate and stored in the auxiliary reactantchamber 50′, will be allowed to react with the main reactant 29′,constituting the second of the two reactants required for the chemicalreaction to activate and stored in the main reactant chamber 28′. Theresulting activation of the chemical reaction is caused by the mutualcontacting of the reactants. The reaction yields the cooling effect.

FIG. 9 a shows a self-cooling container 10 ^(IX) similar to theself-cooling container 10 ^(IV) of FIGS. 4 a-b, however comprising acooling device 20 ^(IX) being made completely of polymeric material. Thecooling device 20 ^(IX) constitutes a polymeric cylinder having threeparts, the first part being a rigid cylinder part 80 which is fixated tothe lid 16 of the beverage can 12′. The lid 16 is gas tight, thus notproviding any fluid communication between the outside and the upperrigid cylinder part 80. The upper rigid cylinder part 80 protrudes intothe beverage can 12′ and is connected to the second cylinder partconstituting an intermediate flexible cylinder 82, which is in turnconnected to the third cylinder part constituting a lower rigid cylinderpart 81, which is sealed off close to the beverage can base 14. Theupper rigid cylinder part 80 constitutes a water chamber 44′ and thelower rigid cylinder part 81 is filled with a reactant granulate. Whenthe beverage can 12′ is filled and pressurised, the pressure will causethe intermediate flexible cylinder 82 to be squeezed off, forming asqueeze off valve, due to the lower pressure inside the cooling device20 ^(IX) compared to the pressure in the beverage can 12′.

FIG. 9 b shows the self-cooling container 10 ^(IX) of FIG. 9 a when thebeverage can 12′ has been opened. The lower pressure in the beverage can12′ will cause the intermediate flexible cylinder 82 to assume anon-squeezed state allowing fluid communication between the upper rigidcylinder part 80 and the lower rigid cylinder part 81. This way theintermediate cylinder 82 forms a channel so that the water contained inthe upper rigid cylinder part will flow into the lower rigid cylinderpart, thereby activating the coated granulate reactant stored in thelower rigid cylinder part 81.

FIG. 9 c shows the self-cooling container 10 ^(IX) comprising a beveragecan 12′ having a cooling device 20 ^(IX) similar to FIG. 9 a and FIG. 9b, however, additionally providing an optional circumferential grippingmember 83 located on the inner wall on the intermediate flexiblecylinder 82. The gripping member 83 is accommodating a separationelement 84 constituting a small disc shaped element of plastic material,which provides a more secure sealing between the water stored in theupper rigid cylinder part 80 and the reactant granulate stored in thelower rigid cylinder part 81. The gripping member 83 and the separationelement 84 are preferably made of substantially rigid plastics. Thegripping member 83 comprise gripping elements which may interlock withcorresponding beads on the separation element 83.

FIG. 9 d shows a close-up of the gripping member 83 and the separationelement 84 of FIG. 9 c when the beverage can 12′ is an unopened andpressurised state.

FIG. 9 e shows a close-up view of FIG. 9 d, when the beverage can 12′has been opened and the reduced pressure from the outside of theintermediate flexible cylinder 82 causes the walls of the intermediateflexible cylinder 82 to separate and causes the separation element 84 todetach from the gripping member 83, thus allowing fluid communicationbetween the upper rigid cylinder part 80 and the lower rigid cylinderpart 81. By using the gripping member 83 and the separation element 84,a well defined separation is accomplished between the upper rigidcylinder part 80 and the lower rigid cylinder part 81 when the coolingdevice 20 ^(IX) is activated and the walls of the intermediate flexiblecylinder 82 are separated.

FIG. 10 a shows a self-cooling container 10 ^(X) similar to theself-cooling container 10 ^(V) of FIGS. 5 a-b. The cooling device 20^(X) has an auxiliary reactant chamber 50′, which is located between thewater chamber 44′ and the main reactant chamber 28′. The auxiliaryreactant chamber 50′ is separated from the main reactant chamber 28′ bya main cap 60′ and a main cap seat 62′. The auxiliary reactant chamber50′ is separated from the water chamber 44′ by an auxiliary cap 86 andan auxiliary cap seat 88. The main cap seat 62′ and the main cap 60′ aswell as the auxiliary cap seat 88 and the auxiliary cap 86 work in thesame way as the main cap seat 62 and the main cap 60 described inconnection with FIGS. 5 a-b.

FIG. 10 b shows the self-cooling container 10 ^(X) of FIG. 10 a when thebeverage can 12′ has been opened and the bottom 22′ of the coolingdevice 20 ^(X) has been caused to bulge outwardly due to the reducedpressure inside the beverage can 12′. This causes the auxiliary cap 86and the main cap 60′ to fall downwardly in direction towards the bottom22′ due to the pressure force, which causes the water, the auxiliaryreactant and the main reactant to mix and thereby activate the chemicalreaction.

FIG. 11 a shows a self-cooling container 10 ^(XI) similar to theself-cooling container 10 ^(X) described in connection with FIGS. 10a-b, however, instead of an auxiliary cap seat and an auxiliary cap, asupport mesh 66 and a rupturable diaphragm 54′ are provided. The supportmesh 66 and the rupturable diaphragm 54′ work in the same as in thepreviously described self-cooling container 10 ^(VI) of FIGS. 6 a-b.

FIG. 11 b shows the self-cooling container 10 ^(XI) of FIG. 11 a whenthe beverage can 12′ has been opened and the cooling device 20 ^(XI) hasbeen activated.

FIG. 12 a and FIG. 12 b show a self-cooling container 10 ^(XII) similarto the self-cooling container 10 ^(X), where the rupturable diaphragm 54and the piercing element 56 of FIGS. 4 a-b have been combined with thesupport mesh 66 and the rupturable diaphragm 54′ of FIGS. 6 a-b.

FIG. 13 a shows a self-cooling container 10 ^(XIII) comprising abeverage can 12″ having a submerged cooling device 20 ^(XIII)constituting a cooling widget. The cooling device 20 ^(XIII) defines acylinder of preferably polymeric material, which may move freely in thebeverage inside the beverage can 12″. The cooling device 20 ^(XIII)comprises a pressure space 32″, a water chamber 44″ and a main reactantchamber 28″. The pressure space 32″ comprises a pressure inlet 52′ forallowing a small amount of beverage to enter the cooling device20^(XIII). The pressure space 32″ and the water chamber 44″ are separatedby a flexible diaphragm 30″. The water chamber 44″ and the main reactantchamber 28′ are separated by a plug seat 90 and a main plug 88 centrallylocated in the plug seat 90. The plug seat 90 seals between the mainplug 88 and the inner wall of the cooling device20 ^(XIII). The mainplug 88 is connected to the flexible diaphragm 30″. The overpressure inthe beverage can 12″ keeps the diaphragm 30″ in a relaxed andnon-activated state. The main plug 88 separates the water in the waterchamber 44″ and granulates reactants in the main reactant chamber 28″.

FIG. 13 b shows the self-cooling container 10 ^(XIII) as described inFIG. 13 a when the beverage can 12″ has been opened. When the beveragecan 12″ has been opened, the pressure inside the beverage can 12″ andthe pressure space 32″ are reduced and the pressure in the water chamber44″ causes the diaphragm 30″ to bulge towards the pressure inlet 52′.When the flexible diaphragm 30″ bulges towards the pressure inlet 52′,the main plug 88, which is connected to the diaphragm 30″ willdisconnect from the plug seat 90 and fluid communication is accomplishedbetween the water chamber 44″ and the main reactant chamber 28″,allowing water to enter the main reactant chamber 44″ and activate thechemical reaction which is causing the beverage to be cooled.

FIG. 14 a shows a self-cooling container 10 ^(XIV) similar to theself-cooling container 10 ^(XIII) shown in FIGS. 13 a-b, however wherethe cooling device 20 ^(XIV) additionally comprises an auxiliaryreactant chamber 50″ including a reaction control fluid for reducing thereaction time. The auxiliary reactant chamber 50″ is located between thewater chamber 44″ and the main reactant chamber 28″. The water chamber44″ and the auxiliary reactant chamber 50″ are separated by a main plugseat 90 and a main plug 88 and the auxiliary reactant chamber 50″ andthe main reactant chamber 28″ are separated by an auxiliary plug seat 94and an auxiliary plug 92. The auxiliary plug 92 is connected to the mainplug 88.

FIG. 14 b shows the self-cooling container 10 ^(XIV) of FIG. 14 a whenthe beverage can 12″ has been opened. The pressure loss when opening thebeverage can 12″ will cause the diaphragm 30″ to bulge towards thepressure inlet 52′. Since both the main plug 88 and the auxiliary plug92 are connected to the flexible diaphragm 30″, both the water chamber44″ and the auxiliary reactant chamber 50″ will establish fluidcommunication with the main reactant chamber 28″. This causes the waterin the water chamber 44″ and the reaction control fluid in the auxiliaryreactant chamber 50″ to flow into the main reactant chamber 28″, whichis filled with the coated granulate reactant 29. When both the reactantsare mixed together in water, the chemical reaction is activated and thecooling is initiated. The reaction control fluid prolongs the coolingeffect and may be used for e.g. preventing ice formation inside thebeverage can 12″.

FIGS. 15 a and 15 b shows a self-cooling container 10 ^(XV) similar tothe self-cooling container 10 ^(XIV) shown in FIGS. 14 a-b, however,instead of using a flow control fluid, the second reactant 29 is storedin the auxiliary reactant chamber 50″, thereby excluding the use of acoating of the reactant. When activation is established by opening thebeverage can 12″ and the first granulate reactant 29′ in the mainreactant chamber 28″ is mixed with the second granulate reactant 29 in awater solution, the chemical reaction is activated.

FIG. 16 a shows a self-cooling container 10 ^(XVI) constituting acooling box comprising an insulating carrier 96 being made of rigidinsulating material, such as Styrofoam or the like. The insulatingcarrier 96 has a cavity 97 defining a space suitable for accommodatingsix standard beverage cans 12′″, i.e. typically sized beverage canshaving a shape corresponding to the beverage cans described above anddesignated the reference numeral 12, however exclusive of the coolingdevice. The inner cavity 97 defines a flat bottom surface and an innercontinuous sidewall which has bulges 98 for defining a plurality ofinterconnected arcs corresponding to the outer surface of six beveragecans defining positions for individual placement of the beverage cans12′″ when placed in the well known 3×2 “sixpack” configuration so that astable and secure positioning is achieved. The inner cavity 97 is thusconfigured for accommodating six beverage cans 12′″ in two rows withthree beverage cans 12′″ in each row (FIG. 16 b). A spacer 99 isprovided for filling up the inner cavity 97 between the six beveragecans 12′″ for added stability. The spacer 99 is preferably made in anon-thermal insulating or weakly thermal insulating material such asplastics, metal or cardboard. In the self-cooling container 10 ^(XVI),one of the beverage cans 12′″ has been substituted by a cooling device20 ^(XVI) having an external shape corresponding to a beverage can 12′″.The cooling device 20 ^(XVI) has an activation button 100, which ispressed for activating the chemical reaction inside the cooling device20 ^(XVI). The inside of the cooling device 20 ^(XVI) may correspond toany of the previous cooling devices shown in FIGS. 1 a, 1 b, 1 c-15 a,15 b, except that the activation is performed by a mechanical actionfrom the outside, i.e. by pressing the activation button 100. Theactivation button 100 may be directly coupled to e.g. a rupturablediaphragm or the like separating the two reactants, thus by pressing theactivation button 100, the diaphragm is ruptured allowing the tworeactants to contact each other. Alternatively the activation button 100may be acting on a pressure space, and the change of pressure causes aflexible diaphragm to move and start the chemical reaction.

FIG. 16 b shows a top view of the self-cooling container 10 ^(XVI)comprising the insulating carrier 96 accommodating the five beveragecans 12 and the cooling device 20 ^(XVI). The self-cooling container 10^(XVI) may be stored at room temperature. When the beverage in thebeverage cans is about to be consumed, the activation button 100 on thecooling device 20 ^(XVI) is pressed and the cooling is activated. Anoptional cover on the insulation carrier 96 may be provided as anadditional insulation.

FIG. 17 a shows a self-cooling container 10 ^(XVII) constituting analternative configuration of the self-cooling container 10 ^(XVI). Thecooling device 20 ^(XVII), corresponding to the cooling device 20 ^(XVI)of FIG. 16 a-b, is accommodated in a centrally located spacer 99′ and 6beverage containers are accommodated in an insulation carrier 96′surrounding the spacer 99′. The insulation carrier 96′ has a roundedouter shape and an inner cavity 97′ having bulges 98′ for accommodatingthe six beverage cans 12′″ in a circumferential configuration around thecentrally located spacer 99′.

FIGS. 17 b and 17 c show a perspective view and a top view,respectively, of the self-cooling container 10 ^(XVII) of FIG. 17 a.

FIGS. 18 a-f show the steps of filling and pressurising a beverage can12 of the type shown in the FIGS. 1 a-c to 3 a-c, including a coolingdevice 20 of the type shown in FIGS. 1 a, 1 b, 1 c-3 a, 3 b, 3 c.

FIG. 18 a shows the process of ventilating the beverage can 12 prior tofilling. The beverage can 12 includes a cooling device 20 and a lidflange 104. The beverage can 12 is typically ventilated three times byinserting a ventilating hose 102 and injecting carbon dioxide (CO₂) intothe beverage can 12. The carbon dioxide will substitute the air insidethe beverage can 12. Any amount of residual air inside the beverage can12 may result in deterioration of the beverage. Subsequent to theventilation, the beverage can 12 is filled with beverage as shown inFIG. 18 b.

FIG. 18 b shows the beverage filling process, in which a filling hose103 is inserted and beverage is injected into the beverage can 12. Thebeverage is pre-carbonated and having a low temperature of just a fewdegrees centigrade above the freezing point for accommodating a maximumamount of carbon dioxide dissolved in the beverage.

FIG. 18 c shows the filled beverage can 12 when the filling hose 103 hasbeen removed. The beverage is kept in a carbon dioxide atmosphere havinga temperature just above the freezing point to be able to be saturatedwith carbon dioxide without the need of a high pressurized environment.

FIG. 18 d shows a beverage can 12, where a lid 16 has been sealed on tothe lid flange 104. The lid 16 is folded on to the lid flange 104forming a pressure tight sealing.

FIG. 18 e shows the beverage can 12 inside a pasteurisation plant 106.The pasteurisation plant 106 comprises a water bath of about 70 degreescentigrade. The pasteurisation process is well known for retarding anymicrobiological growth in food products. During pasteurisation, thepressure inside the beverage can will rise to about 6 bar due to theheating of the beverage and the resulting release of carbon dioxide fromthe beverage. The cooling device 20 should be made sufficiently rigid tobe able to withstand such high pressures. In addition, the reactantsused inside the cooling device 20 should remain unaffected of theincreased temperature and pressure, i.e. they should not combust, react,melt, boil or otherwise change their state making a later initiation ofthe reaction impossible or ineffective. It should also be noted that fornon-pasteurised beverages, such as mineral water, the reactants shouldstill remain unaffected up to a temperature of at least 30 to 35 degreescentigrade, which is a temperature which may be achieved during indooror outdoor storage.

FIG. 18 f shows the beverage can 12 at room temperature. The pressureinside the beverage can 12 is about 3 to 5 bar, which is sufficient forpreventing activation of the cooling device 20. When the beverage can isbeing opened, the pressure inside will escape to the surroundingatmosphere, the beverage can 12 will assume atmospheric pressure of 1bar and the cooling device 20 will activate as previously discussed inconnection with FIGS. 1 a, 1 b, 1 c-15 a, 15 b.

FIGS. 19 a-f show the steps of filling and pressurising a beverage can12 of the type shown in the FIGS. 13 a-b to 15 a-b, including a coolingdevice 20 of the type shown in FIGS. 13 a-b to 15 a-b. The process issimilar to the filling process described above in connection with FIGS.18 a-f, except for the positioning of the cooling device 20 in FIG. 19c, which occurs after filling but before applying the lid 16.

FIGS. 20 a to 20 f show the steps of filling and pressurising a beveragecan 12 of the type shown in the FIGS. 4 a-b to 12 a-b, including acooling device 20 of the type shown in FIGS. 4 a-b to 12 a-b. As thecooling device 20 is attached to the lid 16, the cooling device 20 andthe lid 16 are attached to the beverage can 12 in one piece in FIG. 20d.

FIG. 21 a shows a party keg system 110 having a built-in pressurisationsystem and a self-cooling beverage container. The party keg system 110constitutes a simple beverage dispensing system for typically single useand accommodates about three to ten litres of beverage and typicallyfive litres of beverage. Party kegs are often used for minor socialevents such as private parties and the like. Party kegs often include apressurisation and carbonisation system and one such party keg systemhas been described in the pending and not yet published European patentapplication No. 08388041.9. The party keg mentioned in 08388041.9,however, does not provide any internal cooling, thus requiring externalcooling until the beverage is about to be consumed. The party keg system110 comprises a housing 112, which preferably is made of a lightinsulating material, such as styrofoam or the like. The housing 112comprises an upper space 114 and a lower space 116, which are separatedby a closure 118. A beverage keg 120 including a suitable amount ofbeverage is accommodated in the lower space 116 and fixated to theclosure 118. The beverage keg 120 has an upwards oriented opening 122,which is fixated to the closure 118 by a fixation flange 123. A tappingline 124 is extending through the opening 122 into the beverage keg 120.The tapping line 124 constitutes an ascending pipe and extends throughthe closure 118 via the upper space 114 to the outside of the housing112. Outside the housing 112, a tapping valve 126 is used forcontrolling the flow of beverage through the tapping valve 126. When thetapping valve 126 is in an open position, beverage will flow through thetapping line 124 and leave the party keg system 110 via a beverage tap127, while the beverage may be collected in a glass or the like. Agasket 128 seals the tapping line 124 to the closure 118. A pressuregenerator 130 is located in the upper space 114. The pressure generator130 may be a cartridge of pressurised carbon dioxide or alternatively, achemical pressure generator. The pressure generator 130 is connected tothe beverage keg 120 by a pressurising hose 132. The pressurising hose132 is connected to the interior of the beverage keg 120 via the opening122 and is sealed to the closure 118 by the gasket 128. A pressurisationknob 134 extending between the pressure generator 130 and the outside ofthe housing 112 is used for initiating the pressurisation of thebeverage keg 120. The beverage keg 120 is filled with beverage andadditionally accommodates a cooling device 20 ^(XXI). The cooling device20 ^(XXI) includes a main reactant chamber 28′ and an auxiliary reactantchamber 50″, which are separated by a water-soluble diaphragm 78. Afluid inlet 136 is located next to the water-soluble diaphragm 78. Thefluid inlet 136 will allow pressurised fluid to enter the cooling device20 ^(XXI). The fluid inlet 136 comprise a check valve 138, preventingany reactant from flowing out of the fluid inlet 136 and contact thebeverage due to pressure variations in the beverage keg 120.

FIG. 21 b shows the party keg system 110 of FIG. 21 a when it has beenactivated by operating the pressurisation knob 134. When thepressurisation knob 134 has been operated, pressurised carbon dioxidewill enter the beverage keg 120 and pressurise the beverage accommodatedinside. Beverage will thus enter the fluid inlet 136 of the coolingdevice 20 ^(XXI) and dissolve the water-soluble diaphragm 78. Thiscauses the main reactant 29′ located in the main reactant chamber 28′ tomix with the auxiliary reactant 29 located in the auxiliary reactantchamber 50″ and thereby activate the cooling reaction. The functionalprinciple of the cooling device 20 ^(XXI) is similar to the functionalprinciple of the cooling device 20 ^(VIII) of FIGS. 8 a-b, however, inan opposite direction, i.e., whereas the cooling device 20 ^(VIII) ofFIGS. 8 a-b is initiated by a reduction of pressure, the cooling device20 ^(XXI) of FIGS. 21 a-b is activated by an increase in pressure. Thisway, the party keg system 110 must not be pre-cooled and may be storedat room temperature. When the beverage is about to be consumed, theoperator presses the pressurisation knob, which automatically initiatesthe cooling reaction and after a few minutes, a cool beverage may bedispensed by operating the tapping valve 126. It is further contemplatedthat the housing 112 of the party keg system 110 may be omitted orreplaced by a simpler housing if for instance no insulation is needed.

FIG. 22 a shows a beverage dispensing system 140 for private orprofessional use. Such beverage dispensing systems are well known in theart and have been previously described in the international PCTapplication 2007/019853. The beverage dispensing system 140 comprises apivotable enclosure 142, which is attached to a base plate 144. Theinterior of the enclosure 142 defines a pressure chamber 146. Thepressure chamber 146 is separated from the base plate 144 by a pressurelid 148. The pressure lid 148 is sealed in relation to the base plate144 by sealings 150. The side of the pressure lid 148 facing inwardlytowards the pressure chamber 146 constitutes a coupling flange 152. Thecoupling flange 152 is used for fixating a beverage keg 120′, which isaccommodated within and fills the greater part of the pressure chamber146. The beverage keg 120′ constitutes a collapsible keg which isallowed to collapse due to the pressure force while the beverage isdispensed. A cooling and pressurisation generator 156 is connected tothe pressure chamber 146 for providing cooling and pressurisation forthe beverage located inside the beverage keg 146. A tapping line 124′connects the pressure chamber 146 to a tapping valve 126′. The end ofthe tapping line 124 facing the pressure chamber 146 is provided with acannula 151 for piercing through the coupling flange 152 for allowingfluid communication between the interior of the beverage keg 120′ andthe tapping valve 126′. A tapping handle 154 is used for operating thetapping valve 126′ between the shut-off position and the beveragedispensing position. In the beverage dispensing position, the handle 154is moved from its normal vertical orientation to a horizontalorientation, and beverage is allowed to flow through the tapping valve126′ and leave the beverage dispensing system 140 through a beverage tap127′. The interior of the beverage keg 120′ accommodates beverage and acooling device 20 ^(XXII). The cooling device 20 ^(XXII) which is heldby a fixing rod 158 comprises a main reactant chamber 28 and anauxiliary reactant chamber 50. The main reactant chamber 28 and theauxiliary reactant chamber 50 are separated by a rupturable diaphragm54. The top of the cooling device 20 ^(XXII) is provided with a flexiblediaphragm 30 to which a piercing element 56 is connected. The piercingelement 56 extends towards the rupturable diaphragm 54.

FIG. 22 b shows the beverage dispensing system 140 of FIG. 22 a whereinthe pressure chamber 146 has been pressurised. The pressure in thepressure chamber 146 acts to deform the beverage keg 120″ and causes theflexible diaphragm 30 to bulge inwards towards the rupturable diaphragm54. The rupturable diaphragm 54 will thereby burst by the protrudingpiercing element 56 and the chemical reaction for providing cooling isactivated. This way, a rapid cooling of the beverage inside the beveragekeg 120′ is accomplished and a cold beverage may be dispensed from thebeverage keg 126′ by operating the tapping handle 154 within a fewminutes from activation. This way, the beverage keg 120′ must not becooled and the long waiting period for allowing the beverage to cool ina conventional way is avoided. The cooling device 20 ^(XXII) willrapid-cool the beverage when the beverage keg has been installed.

FIG. 23 a shows a beverage dispensing system 140′ similar to thebeverage dispensing system 140 shown in FIGS. 22 a-b except the coolingdevice 20 ^(XXIII), which works similar to the cooling device 20 ^(XXI)of FIGS. 21 a-b. The cooling device 20 ^(XXIII) comprises a mainreactant chamber 28 and an auxiliary reactant chamber 50, which areseparated by a water-soluble diaphragm 78. The water-soluble diaphragm78 is connected to the coupling flange 152 by an activation channel 160.The coupling flange 152 comprises a dual sealing membrane 162, whichseals the activation channel 160 from the interior of the beverage keg120′ and the outside of the coupling flange 152. FIG. 23 a shows theinstallation procedure of the beverage keg 120′ when the enclosure 142is swung back for allowing access to the pressure chamber 146.

FIG. 23 b shows the beverage dispensing system 140 when the pressure lid148 has been attached to the enclosure 142 and the enclosure 142 hasbeen swung back to the normal position sealing off the pressure chamber146. When the pressure lid 148 is attached, the dual sealing membrane162 is pierced and fluid is allowed to enter the activation channel 160and the tapping line 124′. When the pressure chamber 146 is pressurised,beverage will enter the activation channel 160 and dissolve the watersoluble membrane 78 at the end of the activation channel 160. Thus,activation is accomplished and the chemical reaction will activate forgenerating cooling to the beverage as discussed in connection with FIGS.22 a-b.

FIG. 24 shows a bottle 164 having a bottle cap 166 with an integratedcooling device 20 ^(XXIV). The bottle cap 166 has a cap flange 170 whichis mounted on a threading 168 near the mouth of the bottle 164. Thecooling device 20 ^(XXIV) is fixated to the bottle cap 166 and extendinginto the bottle 164. The cooling device 20 ^(XXIV) has an activationbutton 100′ for activating the cooling before the bottle cap 166 isremoved from the bottle 164.

FIG. 25 shows a bottle 164 having a cooling device 20 ^(XXV) similar tothe cooling device 20 ^(XXIV) shown in FIG. 24 except that a flexiblediaphragm 30 is provided at the top of the cooling device 20 ^(XXV).When the bottle cap 166 is twisted for allowing the pressurised gas toescape from the bottle 164, the flexible diaphragm 30 will bulgeoutwards and thereby initiate the chemical reaction similar to theself-cooling beverage container shown in connection with FIG. 4 a.

FIG. 26 a shows a bottle 164 having the bottle cap 166 and an outer cap172. The outer cap 172 is connected to a tooth rod 176, which is locatedwithin a cooling device 20 ^(XXVI). An intermediate diaphragm 174separates the two reactants within the cooling device20 ^(XXVI).

FIG. 26 b shows the bottle 164 of FIG. 26 a when the outer cap 172 istwisted. By twisting the outer cap 172, the tooth rod 176 ruptures theintermediate diaphragm 174, thereby mixing the two reactants andactivating the chemical reaction for generating cooling. After a fewminutes, the outer cap 172 as well as the bottle cap 166 may be removedand the chilled beverage may be accessed.

FIG. 27 a shows a drink stick 180 constituting a cooling stick having anintegrated cooling device 20 ^(XXVII). The drink stick 180 comprises aknob 182, which may be used as a handle and an elongated flexiblereservoir 184 for accommodating the cooling device 20 ^(XXVII). Thecooling device 20 ^(XXVII) comprises a rupturable reservoir 186comprising a first reactant. A second reactant is accommodated within anelongated flexible reservoir 184 outside the rupturable reservoir 186.

FIG. 27 b shows the activation of the drink stick 180 of FIG. 27 a. Thedrink stick 180 is activated by bending the drink stick 180 in thedirection of the arrows. By bending the drink stick 180, the rupturablereservoir 186 is ruptured and the first reactant is mixed with a secondreactant, thereby activating the chemical reaction generating a coolingeffect.

FIG. 27 c shows the drink stick 180 of FIG. 27 b when the rupturablereservoir 186 has been ruptured and the chemical reaction has beenactivated.

FIG. 27 d shows the drink stick 180 of FIG. 27 c when it has beeninserted into a bottle 164. The bottle 164 may be a conventionalbeverage bottle containing beer or soft drink having a room temperature.Due to the cooling effect of the drink stick 180, the beverage in thebottle 164 is cooled down to temperatures significantly lower than roomtemperature. It is further contemplated that the drink stick 180 may beused with other beverage containers for giving instant cooling to anybeverage. For example the drink stick 180 may be provided in a bar foruse with a chilled long drink, such as gin and tonic, for allowing thedrink to remain cooled for a longer time period.

In an alternative embodiment the above drink stick 180 may have aconical shape and being used together with an ice mould for instantmanufacture of ice cubes by inserting the activated drink stick into thewater filled ice mould. Alternatively, the drink stick may have a cubicshape for direct usage as an ice cube in drinks etc.

FIG. 28 a shows a first embodiment of a bottle sleeve 188 which issuitable for being applied on the outside of a bottle 164 for use ase.g. a wine cooler. The bottle sleeve 188 comprises a main reactantchamber 28 and a water chamber 44, which are separated by a rupturablediaphragm 54. The bottle sleeve 188 is fixated to the bottle by afixation ring 189, which corresponds to a first groove 190 in the bottlesleeve 188. The fixation ring 189 is firmly attached to the bottle 164.The first groove 190 is located juxtaposed the main reactant chamber 28.A second groove 191 is located above the first groove 190 juxtaposed thewater chamber 44.

FIG. 28 b shows the bottle sleeve 188 when it has been activated bypushing it downwards in the direction of the arrows. By pushing thebottle sleeve 188 downwards, the fixation ring 189 will detach from thefirst groove 190 and be accommodated in the second groove 191. Thereby,the rupturable diaphragm 54 will be ruptured by the fixation ring 189and the water in the water chamber 44 will mix with the reactant in themain reactant chamber 28 and the cooling reaction is activated.

FIG. 28 c shows a perspective view of a bottle 164 with an attachedbottle sleeve 188.

FIG. 29 a shows a bottle sleeve constituting a wine cooler 192 in a flatconfiguration. The wine cooler 192 comprises an outer layer 193, aninner layer 194 and the rupturable diaphragm 54 located between theouter layer 193 and the inner layer 194. The space between the outerlayer 193 and the rupturable diaphragm 54 constitutes a water chamber 44and the space between the rupturable diaphragm 54 and the inner layer194 constitutes a main reactant chamber 28. The outer layer 193 and theinner layer 194 are flexible and constitute bistable layers having afirst stable position shown in the flat configuration shown in FIG. 29a.

FIG. 29 b shows the wine cooler 192 in its second bistable positionforming a circular sleeve shape, where the outer layer 193 is facingoutwards and the inner layer 194 is facing inwards. The second stableposition may be accomplished by subjecting the wine cooler 192 to aslight bending force. When the second configuration, i.e. the circularconfiguration is assumed, the rupturable diaphragm 54 is being rupturedand thereby, the water and the reactant are being mixed for generatingcooling.

FIG. 29 c shows the wine cooler 192 in a perspective view.

FIG. 29 d shows the wine cooler 192 being attached to the outside of abeverage bottle 164. The beverage inside the beverage bottle 164 isthereby being efficiently cooled down to a drinking temperature.

It is contemplated that the efficiency of the above self-coolingbeverage containers and cooling devices are strongly dependent on theheat transfer properties (heat transfer factor) of the cooling device.The heat transfer factor may be modified by changing the geometry, inparticular the surface area in beverage contact, of the cooling device,e.g. by providing metal fins onto the cooling device, the heat transferfactor may be increased, thus the cooling efficiency is increased.Consequently, by encapsulating the cooling device in e.g. Styrofoam or ahydrophobic material, the heat transfer factor may be reduced, i.e. thecooling efficiency is decreased. Alternatively, a catalyser may be usedfor increasing the efficiency of the chemical cooling reaction, or anselective adsorption-controlling agent may be used for reducing theefficiency of the chemical cooling reaction.

It is further contemplated that the entire cooling device may be offlexible material, such as rubber or plastics, and itself constitute aflexible diaphragm.

A variant of the cooling device may be activated by pulling a stringconnected to a mixing member through the cooling device.

The cooling device shaped as a pipe within a pipe to cool a beverageflowing through the inner pipe with reaction compartments in the spacebetween the inner pipe and the outer pipe.

The cooling device shaped so as to be mountable around a tapping linefor cooling beverage running through the tapping line.

The cooling device may have a breakable seal to avoid accidentalactivation.

The cooling device containing an arming device, the arming devicecomprising a membrane permeable to the beverage, a saturated saltsolution and a non-permeable membrane separating the salt solution fromthe interior of the cooling device. Upon submersion of the coolingdevice in the container the water from the beverage enters through thepermeable membrane by osmosis into the saturated salt solution whichincreases in volume thus exerting pressure on the membrane which istransmitted to the interior of the cooling device which results inincreased interior pressure which can be used to activate the reactionas described above.

FIG. 30 shows a simplified cubic crystal 195 produced as an insolubleproduct of a non-reversible entropy increasing reaction according to thepresent invention. The crystal 195 has a total of 6 crystal faces, oneof which is designated the reference numeral 196. Furthermore thecrystal 195 defines a total of 8 corners one of which is designated thereference numeral 198. On the crystal faces 196, there are growths, oneof which is designated by the reference numeral 197. On the corners 198growth of the crystal is inhibited by deposits, one of which isdesignated by the reference numeral 199. The deposits are formed from aselective adsorbent selectively adhering to the corners 198 of thecrystal 195. The use of a selective adsorbent for preventing crystalgrowth is indicated in reactions where a non-soluble product mayencapsulate remaining reactants as it is formed thus halting theprocess.

In FIG. 31, a dispensing and refrigerator system according to presentinvention is shown designating the reference numeral 200 in itsentirety. The system comprises a refrigerator cabinet 202 comprising acabinet, in which an inner space is defined as illustrated in the lowerright hand part of FIG. 31 illustrating a cut-away part of therefrigerator cabinet 202 disclosing a plurality of beverage cans, one ofwhich is designated the reference numeral 204, which is supported onbeverage can sliding chutes, one of which is designated the referencenumeral 206 and which supports a total of eight beverage cans 204.Within the refrigerator cabinet 202, a refrigerator unit 208 and aheater unit 210 are enclosed serving the purpose of cooling and heating,respectively, the inner chamber of the refrigerator cabinet 202 forproviding a specific and preset thermostatically controlled temperaturewithin the inner chamber of the refrigerator cabinet 202, such as atemperature of 16°-20° C., in particular a temperature approximately ator slightly above or slightly below the ambient temperature.

Provided the ambient temperature is substantially constant and above acertain lower limit, the heater unit 210 may be omitted, as the innerchamber of the refrigerator cabinet 202 is permanently cooled to atemperature slightly below the ambient temperature. As the innertemperature of the refrigerator cabinet 202 is set at a specificthermostatically controlled temperature, each of the beverage cans 204may contain a cooling device implemented in accordance with theteachings of the present invention for providing a cooling within afairly short period of time, such as a period of time of a few minutes,e.g. 1-5 min., preferably approximately 2 min. from the temperature atwhich the beverage cans are stored within the refrigerator cabinet 202to a specific cooling temperature, such as a temperature of 5° C.

The refrigerator cabinet 202 shown in FIG. 31 is provided with adispensing aperture 212 to which a dispenser chute is connected, whichdispenser chute is designated the reference numeral 216. The system 200shown in FIG. 31 is advantageously provided with additional well-knownelements or components, such as a coin receptor or a card or chip readerfor operating a dispensing mechanism included within the refrigeratorcabinet 202 for controlling the dispensing of the beverage cans 204 fromthe system 200 one at a time after verification of payment orverification of receipt of confirmation of transfer of a specificamount.

By the provision of a thermostatically controlled refrigerator cabinet202, in which the individual beverage cans 204 are stored at a presetand constant temperature, preferably slightly below the ambienttemperature, the overall consumption of electrical energy from the mainsupply is dramatically reduced as compared to a conventional beveragecan dispenser, in which the beverage cans are all cooled to the specificlow temperature of use, i.e. a temperature of e.g. +5° C. for providingto the user a beverage can of a convenient cooled beverage. By thereduction of the cooling to a temperature at or slightly below theambient temperature, only a fraction of the electrical power consumptionis to be used by the beverage dispensing system according to the presentinvention as shown in FIG. 31 as compared to a conventional beverage canrefrigerator and dispenser system. Whereas a convention beverage candispenser and refrigerator system has to cool the beverage cans to atemperature of 5° C. from e.g. an ambient temperature of 25° C. or evenhigher, the system 200 according to the present invention merely servesto cool the beverage cans to a temperature of e.g. 20° C. reducing as arough calculation the energy consumption by at least 80% as compared toa comparable, conventional dispenser and refrigerator system cooling thebeverage cans from 25° C. to 5° C.

In FIG. 32, a refrigerator system according to present invention isshown designated the reference numeral 200′ in its entirety. It is to beunderstood that the beverage dispenser system 200 shown in FIG. 31 maybe modified into a conventional fridge or refrigerator having anopenable front door 203 through which the individual beverage cans 204may be supported on sets of shelves 206′, on which the beverage cans 204are resting and from which the beverage cans 204 may be caught by theusers after opening the refrigerator front door 203.

The refrigerator system 200′ is similar to the refrigerator system 200of FIG. 31 except that the refrigerator system 200′ comprises arefrigerator cabinet door 203 which is openable for exposing theinterior of the refrigerator cabinet. A plurality of beverage bottles,one of which is designated the reference numeral 204′, and kegs, one ofwhich is designated 204″, are supported on beverage can shelves, one ofwhich is designated the reference numeral 206′. The shelves 206′ replacethe chutes 206 of the system described in connection with FIG. 31.Within the refrigerator cabinet 202′, a refrigerator unit 208′ and aheater unit 210′ are enclosed serving the purpose of cooling andheating, respectively, the inner chamber of the refrigerator cabinet202′ for providing a specific and preset thermostatically controlledtemperature within the inner chamber of the refrigerator cabinet, suchas a temperature of 16°-20° C., in particular a temperatureapproximately at or slightly above or slightly below the ambienttemperature.

By cooling the individual beverage cans contained within therefrigerator cabinet or within a conventional fridge as described aboveto a specific and preset temperature, the cooling device included in theindividual beverage can and implemented in accordance with the teachingsof the present invention may be designed to provide a preset andaccurate cooling of the individual beverage can from the temperaturewithin the refrigerator cabinet to the temperature at which the user isto drink or pour the beverage from the beverage can.

Although the invention has above been described with reference to anumber of specific and advantageous embodiments of beverage containers,beverage cans, bottles, cooling devices, dispensing and cooling systemsetc., it is to be understood that the present invention is by no meanslimited to the above disclosure of the above described advantageousembodiments, as the features of the above-identified embodiments of theself-cooling container and also the features of the features of theabove described embodiments of the cooling device may be combined toprovide additional embodiments of the self-cooling container and thecooling device. The additional embodiments are all construed to be partof the present invention. Furthermore, the present invention is to beunderstood encompassed by any equivalent or similar structure asdescribed above and also to be encompassed by the scope limited by thebelow points characterising the present invention and further the belowclaims defining the protective scope of the present patent application.

TABLE 1 Measured cooling per gram of coolant Reactant 1 Reactant 2Reactant 3 Reactant 4 [J/g] Na₂SO₄, 10H₂O MgCl₂, 6H₂0  92 Na₂SO₄, 10H₂OCaCl₂, 6H₂0 148 Na₂SO₄, 10H₂O SrCl₂, 6H₂0 141 Na₂SO₄, 10H₂O Mg(NO₃)₂,6H₂0 106 Na₂SO₄, 10H₂O Ca(NO₃)₂, 4H₂0 172 Na₂SO₄, 10H₂O LiNO₃ 126Na₂SO₄, 10H₂O LiNO_(3,) 3H₂0 — Na₂SO₄, 10H₂O Sr(NO₃), 5H₂0 — MgSO₄, 7H₂0Ca(NO₃)₂, 4H₂0  49 MgSO₄, 7H₂0 SrCl₂, 6H₂0 — KAl(SO₄)₂, 12H₂0 CaCl₂,6H₂0  88 NaAl(SO₄)₂, 12H₂0 CaCl₂, 6H₂0 — NH₄Al(SO₄)₂, 12H₂0 Ca(NO₃)₂,4H₂0 — ZnS0₄, 7H₂0 CaCl₂, 6H₂0  84 Na₂CO₃, 10H₂0 Mg(NO₃)₂, 6H₂0 119Na₂CO₃, 10H₂0 NH₄Cl 240 Na₂CO₃, 10H₂0 NH₄SCN — Na₂CO₃, 10H₂0 NH₄NO₃ —Ba(OH)₂, 8H₂0 NH₄SCN — Sr(OH)₂, 8H₂0 NH₄NO₃ 190 Sr(OH)₂, 8H₂0 NH₄Cl 181Sr(OH)₂, 8H₂0 NH₄NO₃ Mg(NO₃)₂, 6H₂0 183 Sr(OH)₂, 8H₂0 NH₄NO₃ Glysine 173Sr(OH)₂, 8H₂0 NH₄NO₃ NaHCO₃ 176 Sr(OH)₂, 8H₂0 LiOH H₂0 NH₄NO₃ 195Sr(OH)₂, 8H₂0 NH₄SCN 183 Sr(OH)₂, 8H₂0 NH₄NO₃ Na₂SiO_(3,) 9H₂0 H₃BO₃ 204Na₂SiO_(3,) 9H₂0 NH₄NO₃ Sr(OH)₂, 8H₂0 218 Na₂SiO_(3,) 9H₂0 NH₄ClSr(OH)₂, 8H₂0 — Na₂SiO_(3,) 9H₂0 NH₄NO₃ Sr(OH)₂, 8H₂0 NH₄SCN —Na₂SiO_(3,) 9H₂0 NH₄Cl Sr(OH)₂, 8H₂0 NH₄SCN — Na₂SiO_(3,) 9H₂0 NH₄ClSr(OH)₂, 8H₂0 NH₄Al(SO4)_(2,) — 12H₂0 Na₂SiO_(3,) 9H₂0 NH₄NO₃ Mg(NO₃)₂,6H₂0 155 Na₂SiO_(3,) 9H₂0 NH₄NO₃ Ca(NO₃)₂, 4H₂0 128 Na₂SiO_(3,) 9H₂0NH₄SCN 235 Na₂SiO₃, 9H₂0 MgSO_(4,) 7H₂0 NH₄NO₃ 198 KH₂PO₄ CaCl₂, 6H₂0 27 Na₂HPO₄, 12H₂0 CaCl₂, 6H₂0 153 NaH₂PO₄, 2H₂0 CaCl₂, 6H₂0 — NaHCO₃Citric acid H₂0 102 Ca(NO₃)₂, 4H₂0 Oxalic acid NaHCO₃ 147 Ca(NO₃)₂, 4H₂0Oxalic acid KHCO₃ — Ca(NO₃)₂, 4H₂0 Citric acid NaHCO³ —

TABLE 2 Reactant Cooling per mol [kCal/gmol] NH₄Cl 3.82 (NH₄), SO₄, H₂O4.13 H₃BO₃ 5.4 CaCl₂, 6H₂O 4.11 Ca(NO₃)₂, 4H₂O 2.99 Fe(NO₃)₂, 9H₂O 9.1LiCl, 3H₂O 1.98 Mg(NO₃), 6H₂O 3.7 MgSO₄, 7H₂O 3.18 Mn(NO₃)₂, 6H₂O 6.2KAl(SO₄), 12H₂O 10.1 KCl 4.94 KI 5.23 KNO₃ 8.633 K₂C₂O₄ 4.6 K₂C₂O₄, H₂O7.5 K₂S₂O₅, ½H₂O 10.22 K₂S₂O₅ 11.0 K₂SO₄ 6.32 K₂S₂O₆ 13.0 K₂S₂O₃ 4.5Na₂B₄O₇, 10H₂O 16.8 Na₂CO₃, 7H₂O 10.81 Na₂CO_(3,) 10H₂O 16.22 Mal, 2H₂O3.89 NaNO₃ 5.05 NaNO₂ 3.6 Na₃PO₄, 12H₂O 15.3 NaHPO₄, 7H₂O 12.04 Na₂HPO₄,12H₂O 23.18 Na₄, P₂O₇, 10H₂O 11.7 Na₂H₂P₂O₇, 6H₂O 14.0 Na₂SO₃, 7H₂O 11.1Na₂S₂O₆, 2H₂O 11.86 Na₂S₂O₃, 5H₂O 11.30 Sr(NO₃)₂, 4H₂O 12.4 Zn(NO₃)₂,6H₂O 6.0 Acetylorea C₂H₆N₂O₂ 6.812 Benzoic Acid 6.501 Oxagic Acid 8.485Raffinose C₁₈H₃₂O₁₆₁5H₂O 9.7 Kaliumtartrat, 4H₂O 12.342 Urea Oxalat17.806

1-20. (canceled)
 21. A container for storing a beverage, comprising: a container body defining an inner chamber having an inner volume dimensioned to contain a specific volume of a beverage; and a cooling device operatively associated with the container body and having a housing defining a housing volume not exceeding approximately 33% of the specific volume and not exceeding approximately 25% of the inner volume, the cooling device including first and second separate, substantially non-toxic reactants that are capable of reacting with each other to cause a non-reversible, entropy-increasing reaction producing substantially non-toxic products in a stoichiometric number at least a factor of 3 larger than the stoichiometric number of the reactants, wherein the reaction is capable of producing a heat reduction in a beverage contained in the inner chamber of at least about 50 Joules/ml within a period of time of not more than about 5 minutes; wherein the cooling device further includes an actuator operable for initiating the reaction between the first and second reactants.
 22. The container of claim 21, wherein the actuator includes a pressure transmitter operable for transmitting a pressure change within the inner chamber to the cooling device for initiating the reaction in response to the pressure change.
 23. The container of claim 21, wherein each of the reactants is contained within a separate compartment within the cooling device, the compartments being separated by a membrane that is breachable by the actuator.
 24. The container of claim 21, wherein each of the reactants is contained within a separate compartment within the cooling device, the compartments being separated by a plug that is displaceable by the actuator.
 25. The container of claim 21, wherein the container body further comprises a closure for the inner chamber, and wherein the actuator is located outside of the container body and is operable to initiate the reaction through the closure.
 26. The container of claim 21, wherein the reaction produces a volumetric change from the reactants to the substantially non-toxic products of no more than about ±5%.
 27. The container of claim 21, wherein the cooling device is vented to the atmosphere.
 28. The container of claim 21, wherein at least the first reactant is formed of granules having an external coating that allows the reaction of the first reactant with another reactant only in response to the dissolution of the coating by a solvent.
 29. The container of claim 21, wherein the cooling device further includes a chemical activator serving as a reaction-controlling agent.
 30. The container of claim 29, wherein the chemical activator is selected from the group consisting of one or more of water, alcohol, propylene glycol, and acetone.
 31. The container of claim 29, wherein the reaction-controlling agent is a selective adsorption-controlling agent.
 32. The container of claim 29, wherein the reaction-controlling agent is a retardation temperature setting agent.
 33. The container of claim 21, wherein the reactants comprise one or more salt hydrates deliberating in the non-reversible, entropy-increasing reaction a number of free water molecules.
 34. The container of claim 21, further comprising a third separate, substantially non-toxic reactant, wherein the second and third reactants are formed as separate granules, and wherein the first reactant is a coating covering the granules of the second and third reactants.
 35. The container of claim 34, wherein the second and third reactants generate a first non-reversible entropy-increasing reaction producing an intermediate reaction product, and wherein the third reactant reacts with the intermediate reaction product generating a second non-reversible entropy-increasing reaction.
 36. The container of claim 35, wherein the intermediate reaction product is a gas, and wherein the second non-reversible entropy-increasing reaction generates one of a complex and a precipitate.
 37. The container of claim 34, wherein the coating is dissolvable by a solvent, and wherein the first, second and third reactants are reactable with each other only in response to the dissolution of the coating.
 38. The container of claim 21, wherein the cooling device is accommodated within the container body.
 39. A cooling device for use with a container for storing a beverage, the container having a container body including an inner chamber defining an inner volume dimensioned to contain a specific volume of a beverage, the cooling device comprising: a housing defining a housing volume not exceeding approximately 33% of the specific volume and not exceeding approximately 25% of the inner volume; first and second separate, substantially non-toxic reactants that are capable of reacting with one another to produce a non-reversible, entropy-increasing reaction producing substantially non-toxic products in a stoichiometric number at least a factor of 3 larger than the stoichiometric number of the reactants, wherein the reaction is capable of producing a heat reduction in a beverage contained in the inner chamber of at least about 50 Joules/ml within a period of time of not more than about 5 minutes; and an actuator operable for initiating the reaction between the first and second reactants.
 40. The cooling device of claim 39, wherein the actuator includes a pressure transmitter operable for transmitting a pressure change within the inner chamber to the cooling device for initiating the reaction in response to the pressure change.
 41. The cooling device of claim 39, wherein each of the first and second reactants is contained within a separate compartment within the cooling device, the compartments being separated by a membrane that is breachable by the actuator.
 42. The cooling device of claim 39, wherein each of the first and second reactants is contained within a separate compartment within the cooling device, the compartments being separated by a plug that is displaceable by the actuator.
 43. The cooling device of claim 39, wherein the container body further comprises a closure for the inner chamber, and wherein the actuator is located outside of the container body and is operable to initiate the reaction through the closure.
 44. The cooling device of claim 39, wherein the reaction produces a volumetric change from the first and second reactants to the substantially non-toxic products of no more than about ±5%.
 45. The cooling device of claim 39, wherein the cooling device is vented to the atmosphere.
 46. The cooling device of claim 39, wherein at least the first reactant is formed of granules having an external coating that allows the reaction of the first reactant with another reactant only in response to the dissolution of the coating by a solvent.
 47. The cooling device of claim 39, further comprising a chemical activator serving as a reaction-controlling agent.
 48. The cooling device of claim 47, wherein the chemical activator is selected from the group consisting of one or more of water, alcohol, propylene glycol, and acetone.
 49. The cooling device of claim 47, wherein the reaction-controlling agent is a selective adsorption-controlling agent.
 50. The cooling device of claim 47, wherein the reaction-controlling agent is a retardation temperature setting agent.
 51. The cooling device of claim 39, wherein the reactants comprise one or more salt hydrates deliberating in the non-reversible, entropy-increasing reaction a number of free water molecules.
 52. The cooling device of claim 39, wherein the cooling device is configured as a metal can of the size of a beverage can.
 53. The cooling device of claim 39, wherein the cooling device is configured as a box dimensioned to receive a plurality of beverage containers.
 54. The cooling device of claim 39, wherein the cooling device is configured as a stick to be positioned in a beverage bottle.
 55. The cooling device of claim 39, wherein the cooling device is configured as a sleeve to be positioned around a part of a container.
 56. The cooling device of claim 39, wherein the cooling device is configured as a part of a bottle closure. 